TWI890907B - Resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition, a cured product formed by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, and a semiconductor device comprising the cured product or the laminate. The resin composition comprises a cyclized resin or a precursor thereof and a nitrogen-containing compound. The nitrogen-containing compound comprises a nitrogen-containing heterocyclic ring and an amino group in the same compound. One of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

Description

Resin composition, cured product, laminate, method for manufacturing cured product, and semiconductor device

The present invention relates to a resin composition, a cured product, a laminate, a method for manufacturing the cured product, and a semiconductor device.

Cyclized resins such as polyimide have excellent heat resistance and insulation properties, making them suitable for a variety of applications. While these applications are not particularly limited, for example, using semiconductor devices for mounting as an example, they can be used as insulating films, sealing materials, or protective films. They can also be used as base films or cover films for flexible substrates.

For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition comprising at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

This resin composition is applied to a substrate, for example, by coating, to form a photosensitive film. Exposure, development, heating, etc. are then performed as needed to form a cured product on the substrate.

Precursors of the aforementioned cyclized resins, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product.

Resin compositions can be applied using well-known coating methods, offering excellent manufacturing flexibility. For example, the resin composition offers a high degree of design freedom in terms of shape, size, and application location. In addition to the high performance of cyclic resins such as polyimide, this superior manufacturing flexibility is driving increasing anticipation for the industrial application of these resin compositions.

For example, Patent Document 1 describes a resin composition comprising (A) a polyimide precursor, (B) a compound having a heterocyclic structure with a pka of 8.30 to 8.80 and containing a nitrogen atom, and (C) 5-amino-1H-tetrazole.

[Patent Document 1] Japanese Patent Application Publication No. 2020-002281

In components (e.g., devices using such a cured film as an insulating film) that include a cured film made of a cyclic resin such as polyimide and a metal (e.g., a metal layer) in contact with the cured film, it is required that the metal and the cured film be less susceptible to peeling, even over a long period of time.

The present invention aims to provide a resin composition capable of producing a cured product in which separation between the metal and the cured product is unlikely to occur even after a long period of time, a cured product obtained by curing the resin composition, a laminate comprising the cured product, a method for producing the cured product, and a semiconductor device comprising the cured product or the laminate.

Representative examples of the present invention are shown below.

<1> A resin composition comprising a cyclized resin or a precursor thereof and a nitrogen-containing compound, wherein the nitrogen-containing compound contains a nitrogen-containing heterocyclic ring and an amino group in the same compound, wherein one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

<2> The resin composition according to <1>, wherein the nitrogen-containing heterocyclic ring comprises an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton.

<3> The resin composition according to <1> or <2>, wherein the amino group contained in the nitrogen-containing compound is unsubstituted.

<4> The resin composition according to any one of <1> to <3>, wherein the chain length of the linking chain between the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound and the nitrogen atom of the amino group is 3 or less.

<5> The resin composition according to any one of <1> to <4>, wherein the nitrogen atom serving as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound is directly bonded to the carbonyl group.

<6> The resin composition according to any one of <1> to <5>, wherein the nitrogen-containing compound is a compound represented by any one of the following formulas (1-1), (2-1), or (3-1);

In formula (1-1), ^R1 represents a monovalent organic group, ^R1a each independently represents a hydrogen atom or a substituent, and ^RN1 represents a hydrogen atom or a substituent; in formula (2-1), ^R2 represents a monovalent organic group, ^R2a represents a hydrogen atom or a substituent, and ^RN2 represents a hydrogen atom or a substituent; in formula (3-1), ^R3 represents a monovalent organic group, and ^RN3 represents a hydrogen atom or a substituent.

<7> The resin composition according to any one of <1> to <6>, wherein the molecular weight of the nitrogen-containing compound is less than 2000.

<8> The resin composition according to any one of <1> to <7>, which is used to form an interlayer insulating film for a redistribution layer.

<9> A cured product obtained by curing the resin composition described in any one of <1> to <8>.

<10> A laminate comprising two or more layers formed of the hardened material described in <9>, and comprising a metal layer between any of the layers formed of the hardened material.

<11> A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any one of <1> to <8> on a substrate to form a film.

<12> The method for producing a cured product as described in <11>, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.

<13> The method for producing a cured product as described in <11> or <12>, comprising a heating step of heating the film at 50-450°C.

<14> A semiconductor device comprising the cured product described in <9> or the laminate described in <10>.

According to the present invention, there are provided a resin composition capable of producing a cured product in which separation between the metal and the cured product is unlikely to occur even after a long period of time; a cured product formed by curing the resin composition; a laminate comprising the cured product; a method for producing the cured product; and a semiconductor device comprising the cured product or the laminate.

The following describes the main embodiments of the present invention. However, the present invention is not limited to the embodiments described.

In this manual, numerical ranges indicated by the "~" symbol indicate that the numerical values before and after the "~" are included in the range as the lower limit and upper limit, respectively.

In this specification, the term "step" refers not only to independent steps but also to steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.

Regarding the marking of groups (atomic radicals) in this specification, the markings "unsubstituted" and "unsubstituted" include both groups (atomic radicals) without substitution and groups (atomic radicals) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic radiation or radioactive rays.

In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid," and "(meth)acryl" means both or either "acryl" and "methacryl."

In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, the total solid content refers to the total mass of all components of a composition excluding the solvent. Furthermore, in this specification, the solid content concentration refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.

Unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene-equivalent values. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. In cases where THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Unless otherwise specified, GPC measurements utilize UV (ultraviolet) light at a wavelength of 254 nm.

In this specification, when the positional relationship of the layers constituting a laminate is described as "upper" or "lower," it suffices to state that other layers exist above or below the reference layer in the plurality of layers in question. In other words, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer need not be in contact with the other layers. Furthermore, unless otherwise specified, "upper" refers to the direction in which the layers are stacked with respect to the substrate. Alternatively, in the case of a resin composition layer, "upper" refers to the direction from the substrate toward the resin composition layer, and "lower" refers to the opposite direction. Furthermore, this setting of the up and down directions is for the convenience of explaining this manual. In actual practice, the "up" direction in this manual may also be different from the straight-up direction.

In this specification, unless otherwise specified, each component contained in a composition may include two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in a composition represents the total content of all compounds corresponding to that component.

In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.

In this manual, a combination of preferred aspects is considered a more preferred aspect.

(resin composition)

The resin composition of the present invention comprises a cyclized resin or a precursor thereof (hereinafter also referred to as the "specific resin") and a nitrogen-containing compound (hereinafter also referred to as the "specific nitrogen-containing compound"). The specific nitrogen-containing compound contains a nitrogen-containing heterocyclic ring and an amino group in the same compound. One of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent.

The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers.

Furthermore, the resin composition of the present invention can be used to form a photosensitive film for positive-tone development, and can also be used to form a photosensitive film for negative-tone development.

In the present invention, negative-tone development refers to development that removes the unexposed portion during exposure and development, and positive-tone development refers to development that removes the exposed portion during development.

As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, and the developer and development method described in the development step can be used.

The resin composition of the present invention can produce a hardened material that is less likely to peel off between the metal and the hardened material, even over a long period of time.

Although the mechanism by which the above effects are achieved is still unclear, it is speculated as follows.

Traditionally, tetrazoles or aminotetrazoles have been used in cured films to improve adhesion to metals (e.g., Patent Document 1 mentioned above). However, there is still room for improvement in terms of the adhesion between the metal and the cured film over time.

Therefore, the inventors of the present invention have diligently researched and discovered that a cured film with excellent adhesion between metal and cured film over a long period of time can be obtained by using a nitrogen-containing compound (hereinafter referred to as a "specific nitrogen-containing compound"). This nitrogen-containing compound contains a nitrogen-containing heterocyclic ring and an amino group in the same compound. One of the hydrogen atoms of the amino group can be substituted, and the nitrogen atom of the heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

Although the mechanism by which the above effects are achieved is still unclear, it is speculated as follows.

Specific nitrogen-containing compounds, when heated during the formation of the cured film, generate carbonyl, sulfonyl, or thiocarbonyl groups that migrate to amine groups, or decompose at positions such as the carbonyl group to produce compounds that have high metal adsorption properties and form hydrogen or covalent bonds with the polymer. This is presumably responsible for improving the adhesion between the cured film and the metal.

Taking an example of a specific nitrogen-containing compound for illustration, it is speculated that the following specific nitrogen-containing compound, upon heating, migrates as shown in the following formula (S1) or decomposes as shown in the following formula (S2). It is believed that the amide bond contained in the migrated compound in (S1) forms a hydrogen bond with the polymer, and the nitrogen-containing heterocycle forms a complex with the metal, or that the amino group contained in the decomposition product in (S2) forms a covalent bond with the polymer, and the nitrogen-containing heterocycle forms a complex with the metal, thereby improving the adhesion between the cured film and the metal.

[Chemical formula 2]

Furthermore, the specific nitrogen-containing compound before migration or decomposition tends to be dispersed nearly uniformly within the composite film, and its presence near the metal in the cured film increases. Therefore, it is believed that the compound produced after migration or decomposition also tends to be distributed near the metal, resulting in improved adhesion between the cured film and the metal layer.

Furthermore, as mentioned above, the heating during the formation of the cured film causes the specific nitrogen-containing compound to migrate or decompose, generating a compound that has high metal adsorption and forms hydrogen or covalent bonds with the polymer. Therefore, it is speculated that voids are less likely to form at the boundary between the cured film and the metal layer even after a long period of time.

Furthermore, it is believed that the alkalinity of the specific nitrogen-containing compound before migration or decomposition is low, and therefore the storage stability of the composition during storage is also excellent.

However, Patent Document 1 does not describe any specific nitrogen-containing compounds.

The following is a detailed description of the components contained in the resin composition of the present invention.

<Specific resin>

The resin composition of the present invention comprises at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors.

Cyclized resins contain an imide ring structure or Resins with azole ring structures are preferred.

In the present invention, the main chain refers to the relatively longest bond chain in the resin molecule.

As cyclized resins, polyimide, polybenzo Azoles, polyamide imides, etc.

A cyclized resin precursor refers to a resin that undergoes a chemical structural change in response to an external stimulus to become a cyclized resin. Preferably, the resin undergoes a chemical structural change in response to heat, and more preferably, the resin undergoes a ring-closing reaction in response to heat to form a ring structure to become a cyclized resin.

As precursors of cyclized resins, polyimide precursors, polybenzo Azole precursors, polyamide imide precursors, etc.

That is, the resin composition of the present invention comprises a resin selected from polyimide, polyimide precursor, polybenzo Azoles, polybenzo The specific resin is preferably at least one resin (specific resin) selected from the group consisting of azole prodrugs, polyamidoimides, and polyamidoimide prodrugs.

The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.

Furthermore, the specific resin preferably has a polymerizable group, and more preferably contains a free radical polymerizable group.

When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably includes a free radical polymerization initiator described below, and more preferably includes both the free radical polymerization initiator described below and a free radical crosslinking agent described below. Furthermore, a sensitizer described below may be included, if necessary. For example, a negative photosensitive film can be formed from this resin composition of the present invention.

Furthermore, the specific resin may have a polar conversion group such as an acid-degradable group.

When the specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. The resin composition of the present invention can be used to form, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film.

[Polyimide precursor]

The type of polyimide precursor used in the present invention is not particularly limited, but it is preferably a polyimide precursor containing a repeating unit represented by the following formula (2).

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, preferably an oxygen atom.

R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Groups containing linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or combinations thereof are preferred, and groups containing aromatic groups having 6 to 20 carbon atoms are even more preferred. The linear or branched aliphatic groups may be substituted with a group containing a heteroatom in the alkyl group in the chain, and the cyclic aliphatic and aromatic groups may be substituted with a group containing a heteroatom in the alkyl group of a ring member. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, with -Ar-L-Ar- being particularly preferred. Ar is independently an aromatic group, and L is a group including a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a combination of two or more of these. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. A single diamine may be used, or two or more diamines may be used.

Specifically, diamines containing a linear or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof are preferred, and diamines containing an aromatic group with 6 to 20 carbon atoms are even more preferred. The linear or branched aliphatic groups may be substituted with a group containing a heteroatom in the alkyl group within the chain, and the cyclic aliphatic and aromatic groups may be substituted with a group containing a heteroatom in the alkyl group of a ring member. Examples of groups containing aromatic groups include the following.

In the formula, A represents a single bond or a divalent linking group, preferably a group selected from a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, _-SO2- , -NHCO-, or a combination thereof, more preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or _-SO2- , and even more preferably _-CH2- , -O-, -S-, _-SO2- , -C( _CF3 ) _2- , or -C( _CH3 ) _2- .

In the formula, * represents the bonding site with other structures.

Specifically, the diamine includes 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'- Dimethylcyclohexylmethane and isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonium and 3,3'-diaminodiphenylsulfonium, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diaminodiphenyl Methyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonium, bis(4-amino-3-hydroxyphenyl)sulfonium, 4,4'-diaminoterphenyl, 4,4'-bis( 4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl methane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4- Bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethyl) At least one diamine selected from the group consisting of: 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfonium, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotolidine, and 4,4’-diaminoquaternaryl.

Also preferred are diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.

Furthermore, diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the perspective of the flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a combination of two or more of these. Ar is preferably a phenylene group, and L is preferably an aliphatic alkyl group having 1 or 2 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic alkyl group is preferably an alkylene group.

Furthermore, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).

Examples of the monovalent organic group represented by R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[Chemical formula 6]

In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).

Examples of diamines that provide the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

R ¹¹⁵ in formula (2) represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

In formula (5) or formula (6), * independently represents the bonding site with other structures.

In formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a group selected from a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, and -NHCO-, and combinations thereof, more preferably a group selected from a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, and -SO ₂ -, and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and -SO ₂ -.

Specific examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more.

Tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2).

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Also, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can be cited as preferred examples.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ can be exemplified by a residual group of a diaminophenol derivative.

In formula (2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Furthermore, preferably, at least one of R ¹¹³ and R ¹¹⁴ includes a polymerizable group, and more preferably, both include polymerizable groups. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ includes two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, or the like, and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetane group, a benzophenone group, a benzothiazolin ... Azolyl, blocked isocyanate, and amine groups. As the free radical polymerizable group possessed by the polyimide precursor, groups having ethylenically unsaturated bonds are preferred.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

In formula (III), * represents the bonding site with other structures.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkyleneoxy group.

Preferred examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups. Alkylene groups such as ethylene and propylene, -CH ₂ CH(OH)CH ₂ -, cyclohexyl, and polyalkyleneoxy groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred.

In the present invention, a polyalkoxyl group refers to an alkoxyl group directly bonded to two or more groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different.

When the polyalkoxyl group includes multiple alkoxyl groups having different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be random, blocky, or alternating.

The carbon number of the alkylene group (including the carbon number of the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

Furthermore, the above-mentioned alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms.

Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

From the perspective of solvent solubility and solvent resistance, polyalkyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups formed by bonding multiple alkyleneoxy groups to multiple propyleneoxy groups are preferred. Polyalkyleneoxy or polypropyleneoxy groups are more preferred, and polyethyleneoxy is even more preferred. In the aforementioned groups formed by bonding multiple alkyleneoxy groups to multiple propyleneoxy groups, the alkyleneoxy and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred embodiments of the number of repetitions of alkyleneoxy groups in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. However, an acetal group, a ketal group, a silyl group, a silyl ether group, or a tertiary alkyl ester group is preferred. From the perspective of exposure sensitivity, an acetal group or a ketal group is more preferred.

Specific examples of acid-degradable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tert-butoxycarbonylmethyl, and trimethylsilyl ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

Furthermore, the polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). In other words, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased.

In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), respectively, and the preferred ranges are also the same.

R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by formula (2).

As an embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. A total content of 70 mol% or more is more preferred, 90 mol% or more is even more preferred, and more than 90 mol% is particularly preferred. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor, excluding the terminal units, may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000-100,000, more preferably 10,000-50,000, and even more preferably 15,000-40,000. Furthermore, the number average molecular weight (Mn) is preferably 2,000-40,000, more preferably 3,000-30,000, and even more preferably 4,000-20,000.

The molecular weight dispersion of the polyimide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

In this specification, molecular weight dispersion is calculated using weight average molecular weight/number average molecular weight.

Furthermore, when the resin composition includes multiple polyimide precursors as the specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide precursor be within the aforementioned ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersion calculated from the multiple polyimide precursors as a single resin are also within the aforementioned ranges.

[Polyimide]

The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as its main component.

In this specification, alkali-soluble polyimide refers to a polyimide that dissolves 0.1g or more per 100g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C. From the perspective of pattern formation, a polyimide dissolution of 0.5g or more is preferred, and a polyimide dissolution of 1.0g or more is even more preferred. There is no particular upper limit to the dissolution amount, but 100g or less is preferred.

Furthermore, from the perspective of the film strength and insulation properties of the obtained organic film, polyimide having multiple imide structures in the main chain is preferred.

In this specification, "main chain" refers to the longest bond in the polymer molecules that constitute the resin, and "side chain" refers to other bond chains.

-Fluorine Atom-

From the perspective of the film strength of the obtained organic film, it is also preferable that the polyimide contains fluorine atoms.

The fluorine atom is preferably contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below, and is more preferably contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below as a fluorinated alkyl group.

The amount of fluorine atoms is preferably 5% by mass or more, and more preferably 20% by mass or less, relative to the total mass of the polyimide.

-Silicon Atom-

From the perspective of the film strength of the resulting organic film, polyimide containing silicon atoms is also preferred.

The silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described below, for example. It is more preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described below as an organic modified (poly)siloxane structure.

Furthermore, the aforementioned silicon atoms or the aforementioned organically modified (poly)siloxane structures may also be included in the side chains of the polyimide, but are preferably included in the main chain of the polyimide.

The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

-Ethylene unsaturated bond-

From the perspective of the film strength of the obtained organic film, polyimide preferably has ethylenically unsaturated bonds.

Polyimide can have ethylenically unsaturated bonds at the ends of the main chain or on the side chains, but ethylenically unsaturated bonds on the side chains are preferred.

It is preferred that the above-mentioned ethylenically unsaturated bonds have free radical polymerizability.

It is preferred that the ethylenically unsaturated bond is contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below. It is even more preferred that the group having an ethylenically unsaturated bond is contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below.

Among these, it is preferred that an ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the formula (4) described below, and it is more preferred that an ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the formula (4) described below as a group having an ethylenically unsaturated bond.

Examples of groups having ethylenically unsaturated bonds include vinyl, allyl, vinylphenyl, and other groups having vinyl groups that are directly bonded to an aromatic ring and may be substituted, (meth)acryloyl, (meth)acryloyloxy, and groups represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of carbon atoms repeated is 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group obtained by combining two or more of these groups.

Furthermore, the aforementioned alkylene group having 2 to 12 carbon atoms may be any of a linear, branched, ring, or cyclic alkylene group, or a combination thereof.

As the aforementioned alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferred, and an alkylene group having 2 to 4 carbon atoms is more preferred.

Among these, R ²¹ is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene group having 2 to 30 carbon atoms, or a group obtained by bonding two or more of these groups; X represents an oxygen atom or a sulfur atom; * represents a bonding site to another structure; and ● represents a bonding site to the oxygen atom to which ^R21 in formula (IV) is bonded.

In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in ^R21 described above.

In formula (R1), X is preferably an oxygen atom.

In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same.

The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (e.g., 2-isocyanateethyl methacrylate).

The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate).

The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an epoxypropylene group and an ethylenic unsaturated bond (e.g., glycidyl methacrylate).

In formula (IV), * represents the bonding site with other structures, preferably the bonding site with the main chain of polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, and more preferably 0.0005-0.05 mol/g.

-Polymerizable groups other than groups having ethylenically unsaturated bonds-

Polyimide may have polymerizable groups other than groups having ethylenically unsaturated bonds.

Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and cyclohexane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups.

The polymerizable group other than the group having an ethylenically unsaturated bond is preferably contained in, for example, R ¹³¹ in the repeating unit represented by the formula (4) described below.

The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, and more preferably 0.001-0.05 mol/g.

-Polarity conversion base-

The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

The polarity conversion group is included in, for example, R ¹³¹ and R ¹³² in the repeating unit represented by the formula (4) described below, or at the end of the polyimide.

-Acid Value-

When polyimide is subjected to alkaline development, from the perspective of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or greater, more preferably 50 mgKOH/g or greater, and even more preferably 70 mgKOH/g or greater.

Furthermore, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.

When the polyimide is developed using a developer containing an organic solvent as its main component (e.g., "solvent development" described below), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, more preferably 2 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

Furthermore, as the acid groups contained in the polyimide, from the perspective of both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are even more preferred.

pKa is the equilibrium constant Ka expressed as its negative common logarithm, taking into account the dissociation reaction that releases hydrogen ions from the acid. In this specification, unless otherwise specified, pKa values are calculated using ACD/ChemSketch (registered trademark). Alternatively, refer to the values disclosed in the "Chemical Handbook, Basic Edition, Revised 5th Edition," edited by the Chemical Society of Japan.

In addition, when the acid group is a polyacid such as phosphoric acid, the above pKa is the first dissociation constant.

As such acid groups, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-Phenolic hydroxyl-

From the perspective of achieving an appropriate development speed using an alkaline developer, it is preferred that the polyimide have a phenolic hydroxyl group.

Polyimide can have phenolic hydroxyl groups at the ends of the main chain or on the side chains.

The phenolic hydroxyl group is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described below or R ¹³¹ in the repeating unit represented by the formula (4) described below.

The amount of phenolic hydroxyl groups relative to the total mass of the polyimide is preferably 0.1-30 mol/g, and more preferably 1-20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When a polymerizable group is present, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or (4-2), or may be located at the terminal of the polyimide.

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4).

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group; if not a polymerizable group, it is an organic group; and the other groups have the same meanings as in formula (4).

Examples of polymerizable groups include the aforementioned groups containing ethylenically unsaturated bonds or crosslinking groups other than the aforementioned groups containing ethylenically unsaturated bonds.

R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same ones as those for R ¹¹¹ in formula (2), and the preferred range is also the same.

Furthermore, R ¹³¹ includes a diamine residue remaining after removing the amino group of a diamine. Examples of the diamine include aliphatic, cycloaliphatic, or aromatic diamines. Specific examples include R ¹¹¹ in formula (2) of a polyimide precursor.

From the perspective of more effectively suppressing warping during calcination, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains in total in one molecule, or both. Even more preferred is a diamine residue containing no aromatic rings.

Examples of diamines containing two or more ethylene glycol chains or propylene glycol chains in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all product names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as those for R ¹¹⁵ in formula (2), and the preferred range is also the same.

For example, four bonders of the tetravalent organic group exemplified as R ¹¹⁵ bond to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

R ¹³² may include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. A specific example is R ¹¹⁵ in formula (2) of the polyimide precursor. From the perspective of organic film strength, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

At least one of R ¹³¹ and R ¹³² preferably has an OH group. More specifically, preferred examples of R ¹³¹ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the aforementioned (DA-1) to (DA-18). More preferred examples of R ¹³² include the aforementioned (DAA-1) to (DAA-5).

Furthermore, the polyimide preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

Furthermore, in order to improve the storage stability of the resin composition, it is preferred to seal the ends of the polyimide backbone with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monochloride compound, or monoactive ester compound. Among these, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these end-capping agents may be used, and by reacting multiple end-capping agents, multiple different terminal groups can be introduced.

-Imidization rate (ring closure rate)-

Considering the film strength and insulation properties of the resulting organic film, the imidization rate (also known as the "ring closure rate") of the polyimide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

The upper limit of the imidization rate is not particularly limited, as long as it is 100% or less.

The above-mentioned imidization rate is measured, for example, by the following method.

The infrared absorption spectrum of the polyimide was measured to determine the peak intensity P1 at approximately 1377 ^cm⁻¹ , an absorption peak originating from the imide structure. The polyimide was then heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was again measured to determine the peak intensity P2 at approximately 1377 ^cm⁻¹ . The obtained peak intensities P1 and P2 were used to determine the imidization ratio of the polyimide according to the following formula.

Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The polyimide may contain all repeating units represented by the above formula (4) containing one type of R ¹³¹ or R ¹³² , or may contain repeating units represented by the above formula (4) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).

Polyimide can be synthesized by the following methods: a method of reacting tetracarboxylic dianhydride with a diamine (a capping agent in which a portion is substituted with a monoamine) at low temperature; a method of reacting tetracarboxylic dianhydride (a capping agent in which a portion is substituted with an acid anhydride, monochloride compound, or monoactive ester compound) with a diamine at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and reacting the diester with a diamine (a capping agent in which a portion is substituted with a monoamine) in the presence of a condensing agent; a method of reacting tetracarboxylic dianhydride with an alcohol and reacting the diester with a diamine (a capping agent in which a portion is substituted with a monoamine) in the presence of a condensing agent; A polyimide precursor can be obtained by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, chlorinating the remaining dicarboxylic acid, and reacting the resulting product with a diamine (partially substituted with a monoamine end-capping agent) to obtain the polyimide precursor. This product can then be completely imidized using a known imidization method. Alternatively, the imidization reaction can be stopped midway to introduce a partial imide structure. Furthermore, a partial imide structure can be introduced by mixing a fully imidized polymer with the polyimide precursor. Other known polyimide synthesis methods can also be applied.

The weight-average molecular weight (Mw) of the polyimide is preferably 5,000-100,000, more preferably 10,000-50,000, and even more preferably 15,000-40,000. A weight-average molecular weight of 5,000 or higher can improve the folding resistance of the cured film. To achieve an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or higher is particularly preferred.

The number average molecular weight (Mn) of the polyimide is preferably 2,000-40,000, more preferably 3,000-30,000, and even more preferably 4,000-20,000.

The molecular weight dispersion of the polyimide is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyimide is not particularly limited, but is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

Furthermore, when the resin composition includes multiple polyimides as the specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide be within the aforementioned ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersion of the multiple polyimides as a single resin are also within the aforementioned ranges.

Polyphenylene azole prodrugs

Regarding the polyphenylene phthalate used in the present invention The structure of the azole precursor is not particularly limited, but preferably comprises repeating units represented by the following formula (3).

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, it is preferred that at least one of them is a polymerizable group.

In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R ¹²¹ is preferably a dicarboxylic acid residue. The dicarboxylic acid residues may be used alone or in combination.

As the dicarboxylic acid residue, dicarboxylic acids containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, and a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group and two -COOH groups is more preferred. The linear or branched (preferably linear) aliphatic group preferably has a carbon number of 2-30, more preferably 2-25, even more preferably 3-20, even more preferably 4-15, and particularly preferably 5-10. The linear aliphatic group is preferably an alkylene group.

Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetrafluorohexanediol, 2,3-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid, 2,2 ...2-dimethylbutanedioic acid, 2,2-dimethylbutanedioic acid, 2 Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

(In the formula, Z is a alkyl group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As dicarboxylic acids containing aromatic groups, the following dicarboxylic acids having aromatic groups are preferred, and the following dicarboxylic acids containing only aromatic groups and two -COOH groups are more preferred.

[Chemical formula 18]

In the formula, A represents a divalent group selected from the group consisting of _-CH2- , -O-, -S-, _-SO2- , -CO-, -NHCO-, -C( _CF3 ) _2- , and -C( _CH3 ) _2- , and * represents each independently a bonding site with other structures.

Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2), and the preferred range is also the same.

R ¹²² is preferably a group derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfonium, 4,4'-diamino-3,3'-dihydroxydiphenylsulfonium, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and the like. The diaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, the following diaminophenol derivatives having an aromatic group are preferred.

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , or -NHCO-, and * and # each represent a bonding site to another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. Furthermore, ^R122 is preferably a structure represented by the above formula. In the case where R ¹²² has a structure represented by the above formula, among a total of 4 * and #, any 2 are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3) and the other 2 are bonding sites to the oxygen atom bonded to R ¹²² in formula (3). It is preferred that 2 * are bonding sites to the oxygen atom bonded to R ¹²² in formula (3) and 2 # are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3). Or, 2 * are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3) and 2 # are bonding sites to the oxygen atom bonded to R ¹²² in formula (3). It is more preferred that 2 * are bonding sites to the oxygen atom bonded to R 122 in formula (3). It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

The diaminophenol derivative is preferably a compound represented by formula (A-s).

In formula (As), _R1 is an organic group selected from a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or the group represented by the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

(In formula (A-sc), * represents an aromatic ring bond to the aminophenol group of the bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (As), having a substituent at the adjacent position to the phenolic hydroxyl group, i.e., at _R3 , is considered particularly advantageous in that it brings the carbonyl carbon of the amide bond and the hydroxyl group closer together, further enhancing the effect of achieving a high cyclization rate during curing at low temperatures.

In the above formula (As), it is preferred that R ₂ and R ₃ are both alkyl groups because they can maintain high transparency to i-rays and exhibit a high cyclization rate during curing at low temperatures.

In the above formula (As), _R1 is preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, polyphenylene oxides having an excellent balance of high transparency to I-rays and a high cyclization rate during curing at low temperatures can be obtained while having sufficient solubility in solvents. From the perspective of azole prodiols, -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferred.

For methods of producing the bisaminophenol derivative represented by formula (A-s), reference can be made, for example, to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506, the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070-0080 of Japanese Patent Application Laid-Open No. 2013-256506, which are incorporated herein by reference. Of course, the present invention is not limited to these examples.

polybenzo In addition to the repeating units of formula (3), the azole precursor may also contain other types of repeating units.

In terms of being able to suppress the warp associated with ring closure, polyphenylene sulfide The azole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[Chemical formula 22]

a: b:

In formula (SL), Z has an a-structure and a b-structure, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining groups are hydrogen atoms or organic groups having 1 to 30 carbon atoms, and may be the same or different. The polymerization of the a-structure and the b-structure can be block or random. The molar percentage of the Z portion is 5 to 95 molar percent for the a-structure, 95 to 5 molar percent for the b-structure, and a + b equals 100 molar percent.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the polyphenylene oxide can be more effectively reduced. The elastic modulus of the azole prodrug after dehydration and ring closure can take into account both the effect of suppressing warp and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such a tetracarboxylic acid residue include R ¹¹⁵ in formula (2).

polybenzo The weight average molecular weight (Mw) of the azole prodrug is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

The above-mentioned polybenzo The molecular weight dispersion of the azole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit on the molecular weight dispersion of the azole prodrug. For example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is even more preferred, 2.3 or less is even more preferred, and 2.2 or less is even more preferred.

Furthermore, the resin composition contains a plurality of polybenzoic acid In the case of an azole precursor as a specific resin, at least one polybenzoic acid The weight average molecular weight, number average molecular weight and dispersion of the azole precursor are preferably within the above ranges. The weight average molecular weight, number average molecular weight, and dispersity of the azole prodrug calculated as one resin are preferably within the above ranges.

Polyphenylene azole

As polyphenylene sulfide Azoles, as long as they have benzo The polymer compound containing an azole ring is not particularly limited, but compounds represented by the following formula (X) are preferred, and compounds represented by the following formula (X) having a polymerizable group are even more preferred. The polymerizable group is preferably a free radical polymerizable group. Alternatively, compounds represented by the following formula (X) having a polar conversion group such as an acid-decomposable group may be used.

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

In the case of having a polar conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the acid-decomposable group may be located on at least one of R ¹³³ and R ¹³⁴ , as shown in the following formula (X-1) or formula (X-2), or may be located on the polyphenylene glycol. The end of the azole.

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group or a polarity-converting group such as an acid-degradable group; if not, it is an organic group; and the other groups have the same meanings as in formula (X).

In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The other groups have the same meanings as in formula (X).

The polymerizable group or polarity-converting group such as an acid-degradable group has the same meaning as the polymerizable group described above for the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include aliphatic groups and aromatic groups. Specific examples include polyphenylene glycol. Examples of R ¹²¹ in the formula (3) of the azole prodigy. Preferred examples are the same as those for R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include polyphenylene glycol and polyphenylene glycol. Examples of R ¹²² in the formula (3) of the azole prodiol are shown below. Preferred examples are the same as those for R ¹²² .

For example, the four bonders of the tetravalent organic group exemplified as ^R122 bond to the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring. For example, when ^R134 is the following organic group, the following structure is formed. In the following structures, * represents the bonding site to the nitrogen atom or oxygen atom in formula (X).

polybenzo Azoles The azole rate is preferably 85% or more, and more preferably 90% or more. The upper limit is not particularly limited and can be 100%. The azole rate is more than 85%, which is achieved by heating The ring closure produced during azole treatment reduces membrane contraction, thus more effectively suppressing warping.

above The oxazolidinylation rate is measured, for example, by the following method.

Determination of polyphenylene sulfide The infrared absorption spectrum of the polybenzophenone was obtained, and the peak intensity Q1 at about 1650 cm ^-1 , which is the absorption peak of the amide structure derived from the precursor, was determined. Then, the absorption intensity of the aromatic ring found at about 1490 cm ^-1 was normalized. After heat treatment of the azole at 350°C for 1 hour, the infrared absorption spectrum was measured again to determine the peak intensity Q2 at around 1650 cm ^-1 and normalize it with the absorption intensity of the aromatic ring found at around 1490 cm ^-1 . Using the obtained standard values of the peak intensities Q1 and Q2, the polyphenylene glycol (PPG) can be determined according to the following formula: Azoles Azolation rate.

Azolation rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) × 1 00

polybenzo The azole may contain all repeating units of the above formula (X) containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (X) containing two or more different types of R ¹³¹ or R ¹³² . In addition to the repeating units of the above formula (X), azoles may also contain other types of repeating units.

About polyphenylene sulfide For example, a polybenzoxazole is obtained by reacting a diaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acids. azole prodrugs, and utilizing known Azolation reaction Obtained by azole.

Furthermore, in the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives obtained by pre-reacting with 1-hydroxy-1,2,3-benzotriazole, etc., can be used to improve the reaction yield.

polybenzo The weight average molecular weight (Mw) of the azole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In the case of azoles, at least one polybenzo The weight average molecular weight of the azole is preferably within the above range.

Also, polyphenylene sulfide The number average molecular weight (Mn) of the azole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.

The above-mentioned polybenzo The molecular weight dispersion of polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersion of azole is not particularly limited, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and even more preferably 2.2 or less.

Furthermore, the resin composition contains a plurality of polybenzoic acid In the case of azole as a specific resin, at least one polybenzo The weight average molecular weight, number average molecular weight and dispersion of the polybenzoxazole are preferably within the above ranges. The weight average molecular weight, number average molecular weight, and dispersity of the azole calculated as one resin are preferably within the above ranges.

[Polyamide imide precursor]

The polyamide imide precursor preferably comprises a repeating unit represented by the following formula (PAI-2).

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by linking two or more of these groups via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by two or more of these groups. -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by two or more of these groups is more preferred.

As the aforementioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred.

The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogenated alkylene group include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. The halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms. However, halogenated alkylene groups are preferably substituted with halogen atoms. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl)methylene.

As the arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

Furthermore, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferred.

In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.

Two of the three carboxyl groups in the above tricarboxylic acid compound can be converted to anhydride.

Examples of halogenated tricarboxylic acid compounds used in the production of polyamide imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, the tricarboxylic acid compound is preferably one containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferably, the tricarboxylic acid compound contains an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of tricarboxylic acid compounds include compounds in which 1,2,3-propanetricarboxylic acid, 1,3,5- _{pentanetricarboxylic} acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C( _CH3 ) _2- , -C( _CF3 ) _2- , _-SO2- , or a phenylene group.

These compounds may be compounds in which two carboxyl groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in formula (2), respectively, and preferred embodiments thereof are also the same.

The polyamide imide precursor may further comprise other repeating units.

As other repeating units, there can be cited the repeating unit represented by the above formula (2), the repeating unit represented by the following formula (PAI-1), etc.

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.

In formula (PAI-1), R ¹¹⁶ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by linking two or more of these groups via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by two or more of these groups. -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by two or more of these groups is more preferred.

As the aforementioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred.

The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogenated alkylene group include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. The halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms. However, halogenated alkylene groups are preferably substituted with halogen atoms. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl)methylene.

As the arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is even more preferred.

Furthermore, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide.

In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dihalogenated dicarboxylic acid compound.

The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, preferably chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalides used in the production of polyamide imide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides.

These dicarboxylic acid compounds or dicarboxylic acid dihalides may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or a linking group. More preferably, the dicarboxylic acid compound or dicarboxylic acid dihalide contains an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexafluorodecanedioic acid, and 2,2,6,6-tetramethylpimelic acid. Diacid, 1,9-azeladic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, trisicosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, Nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4’-biphenylcarboxylic acid, 4,4’-biphenylcarboxylic acid, 4,4’-dicarboxyldiphenyl ether, benzophenone-4,4’-dicarboxylic acid, etc.

Specific examples of dicarboxylic acid dihalides include compounds having a structure in which two carboxyl groups of the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2), and the preferred embodiment is also the same.

Furthermore, the polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyamide imide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

As an embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited. All the repeating units in the polyamide-imide precursor, excluding the terminal units, may be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).

Another embodiment of the polyamide-imide precursor of the present invention includes an embodiment in which the combined content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or greater of all repeating units. This combined content is more preferably 70 mol% or greater, even more preferably 90 mol% or greater, and particularly preferably greater than 90 mol%. There is no particular upper limit to this combined content; all repeating units in the polyamide-imide precursor, excluding the terminal units, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyamide-imide precursor is not particularly specified; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple polyamide-imide precursors as the specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide-imide precursor fall within the above ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersity calculated from the aforementioned multiple polyamide imide precursors as one resin are within the aforementioned ranges.

[Polyamide imide]

The polyamide imide used in the present invention may be an alkali-soluble polyamide imide or a polyamide imide soluble in a developer containing an organic solvent as its main component.

In this specification, alkali-soluble polyamide imide refers to a 2.38 mass% solution of tetramethylammonium hydroxide aqueous solution per 100g of polyamide imide. An aqueous solution of tetramethylammonium hydroxide at 23°C dissolves at least 0.1g of polyamide imide. From the perspective of pattern formation, dissolution of at least 0.5g of polyamide imide is preferred, and dissolution of at least 1.0g of polyamide imide is even more preferred. The upper limit of the dissolution amount is not particularly limited, but 100g or less is preferred.

Furthermore, from the perspective of the membrane strength and insulation properties of the obtained organic membrane, the polyamide imide preferably has multiple amide bonds and multiple imide structures in the main chain.

-Fluorine Atom-

From the perspective of the film strength of the obtained organic film, polyamide imide preferably has fluorine atoms.

The fluorine atom is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below, and is more preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below as a fluorinated alkyl group.

The amount of fluorine atoms is preferably 5% by mass or more, and more preferably 20% by mass or less, relative to the total mass of the polyamide imide.

-Ethylene unsaturated bond-

From the perspective of the film strength of the resulting organic film, the polyamide imide may have ethylenically unsaturated bonds.

Polyamide imide can have ethylenically unsaturated bonds at the ends of the main chain or on the side chains, but ethylenically unsaturated bonds on the side chains are preferred.

It is preferred that the above-mentioned ethylenically unsaturated bonds have free radical polymerizability.

Preferably, an ethylenically unsaturated bond is contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below. More preferably, a group having an ethylenically unsaturated bond is contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below.

Preferred embodiments of the group having an ethylenically unsaturated bond are the same as those of the group having an ethylenically unsaturated bond in the aforementioned polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of the polyamide imide is preferably 0.0001-0.1 mol/g, and more preferably 0.001-0.05 mol/g.

-Polymerizable groups other than ethylenically unsaturated bonds-

Polyamide imide may have polymerizable groups other than ethylenically unsaturated bonds.

Examples of polymerizable groups other than ethylenically unsaturated bonds in the polyamide imide include the same polymerizable groups other than ethylenically unsaturated bonds in the aforementioned polyimide.

The polymerizable group other than the ethylenically unsaturated bond is preferably contained in R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below.

The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamide imide is preferably 0.05-10 mol/g, and more preferably 0.1-5 mol/g.

-Polarity conversion base-

The polyamide imide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamide imide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid Value-

When the polyamide imide is subjected to alkaline development, from the perspective of improving developability, the acid value of the polyamide imide is preferably 30 mgKOH/g or greater, more preferably 50 mgKOH/g or greater, and even more preferably 70 mgKOH/g or greater.

Furthermore, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.

When the polyamide imide is developed using a developer containing an organic solvent as a main component (e.g., "solvent development" described below), the acid value of the polyamide imide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

Furthermore, as the acid groups contained in the polyamide imide, the same groups as the acid groups in the above-mentioned polyimide can be cited, and the preferred embodiments are also the same.

-Phenolic hydroxyl-

From the perspective of achieving an appropriate development speed using an alkaline developer, it is preferred that the polyamide imide have a phenolic hydroxyl group.

Polyamide imide can have phenolic hydroxyl groups at the ends of the main chain or on the side chains.

The phenolic hydroxyl group is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described below.

The amount of phenolic hydroxyl groups relative to the total mass of the polyamide imide is preferably 0.1-30 mol/g, and more preferably 1-20 mol/g.

The polyamide imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

[Chemical formula 29]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.

When a polymerizable group is present, the polymerizable group may be located on at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at the terminal of the polyamide imide.

Furthermore, to improve the storage stability of the resin composition, it is preferred to cap the ends of the polyamide imide backbone chain with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monochloride compound, or monoactive ester compound. Preferred embodiments of the capping agent are the same as those for the polyimide described above.

-Imidization rate (ring closure rate)-

Considering the film strength and insulation properties of the resulting organic film, the imidization rate (also known as the "ring closure rate") of the polyamide imide is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

The upper limit of the imidization rate is not particularly limited, as long as it is 100% or less.

The above-mentioned imidization rate is measured by the same method as the ring closure rate of the above-mentioned polyimide.

The polyamidoimide may contain all repeating units represented by the above formula (PAI-3) containing one type of R ¹¹¹ or R ¹¹⁷ , or may contain repeating units represented by the above formula (PAI-3) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyamidoimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

Polyamide imide can be synthesized, for example, by obtaining a polyamide imide precursor by a known method and completely imidizing it using a known imidization reaction method; or by stopping the imidization reaction midway to introduce a partial imide structure; or by introducing a partial imide structure by mixing a fully imidized polymer with the polyamide imide precursor.

The weight-average molecular weight (Mw) of the polyamide imide is preferably 5,000-70,000, more preferably 8,000-50,000, and even more preferably 10,000-30,000. A weight-average molecular weight of 5,000 or higher improves the folding resistance of the cured film. To achieve an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred.

Furthermore, the number average molecular weight (Mn) of the polyamide imide is preferably 800-250,000, more preferably 2,000-50,000, and even more preferably 4,000-25,000.

The molecular weight dispersion of the polyamide imide is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyamide imide is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.

Furthermore, when the resin composition includes multiple polyamide imides as the specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide imide be within the aforementioned ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersion calculated for the multiple polyamide imides as a single resin are also within the aforementioned ranges.

[Method for producing polyimide precursors, etc.]

Polyimide precursors can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamide, and then esterifying the obtained product using a condensing agent or an alkylating agent, obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the obtained product in the presence of a diamine and a condensing agent, or obtaining a diester from tetracarboxylic dianhydride and an alcohol, halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the obtained product with a diamine. Among the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the obtained product with a diamine is more preferred.

Examples of the condensation agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.

Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.

Examples of the above-mentioned halogenating agents include thiochloride, oxalyl chloride, and phosphorus oxychloride.

In the production method of polyimide precursors, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more.

The organic solvent can be appropriately selected depending on the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.

In the production method of polyimide precursors, it is preferred to add an alkaline compound during the reaction. The alkaline compound may be one or two or more.

The alkaline compound can be appropriately selected depending on the raw material, but examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-Capping agent-

In the production of polyimide precursors, it is preferred to seal carboxylic anhydrides, anhydride derivatives, or amine groups remaining at the ends of the polyimide precursor resin to further improve storage stability. Capping agents for sealing carboxylic anhydrides and anhydride derivatives remaining at the ends of the resin include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspectives of reactivity and film stability, monoalcohols, phenols, or monoamines are particularly preferred. Preferred monohydric alcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as tertiary butanol and adamantanol. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and the like. Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these end-capping agents may be used, and by reacting multiple end-capping agents, multiple different terminal groups can be introduced.

Furthermore, when sealing the amine groups at the resin terminals, compounds having functional groups that react with the amine groups can be used. Preferred sealants for amine groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred carboxylic acid chloride compounds include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, trimethylacetyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyl chloride, stearyl chloride, and benzoyl chloride.

-Solid precipitation-

The production method of a polyimide precursor may include a solid precipitation step. Specifically, after filtering out the water-absorbing byproducts of the dehydration condensation agent present in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain the polyimide precursor. To increase the degree of purity, the polyimide precursor may be repeatedly subjected to re-dissolution, re-precipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[Content]

The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 40% by mass or greater, and even more preferably 50% by mass or greater, relative to the total solids content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition.

The resin composition of the present invention may contain only one specific resin or two or more. When containing two or more specific resins, the total amount is preferably within the above range.

Furthermore, the resin composition of the present invention preferably contains at least two types of resins.

Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins. However, containing two or more specific resins is preferred.

When the resin composition of the present invention contains two or more specific resins, it is preferred that the resin composition contains two or more polyimide precursors having different structures (R ¹¹⁵ in the above formula (2)) derived from dianhydrides.

<Other resins>

The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter also referred to as "other resins").

Other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxane and silicone structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, and the like.

For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.

For example, by adding a (meth)acrylic resin having a weight-average molecular weight of 20,000 or less and a high polymerizable group value (e.g., a polymerizable group content of 1× ^10-3 mol/g or more per 1g of resin) to the resin composition, instead of or in addition to the polymerizable compound described below, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition.

Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition.

In a preferred embodiment of the resin composition of the present invention, the content of other resins can also be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, relative to the total solids content of the resin composition. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or greater.

The resin composition of the present invention may contain only one other resin or two or more. When two or more resins are included, the total amount is preferably within the above range.

<Specific nitrogen-containing compounds>

The resin composition of the present invention comprises a nitrogen-containing compound that contains a nitrogen-containing heterocyclic ring and an amino group in the same compound. One of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

[Nitrogen-containing heterocyclic ring]

The nitrogen-containing heterocyclic ring in the specific nitrogen-containing compound is a heterocyclic ring containing nitrogen atoms as ring members.

The nitrogen-containing heterocyclic ring may be a monocyclic ring or a bicyclic ring, with monocyclic rings or condensed rings being preferred. A 5-membered or 6-membered monocyclic ring, a condensed ring of 5-membered rings, a condensed ring of 6-membered rings, or a condensed ring of a 5-membered ring and a 6-membered ring is more preferred. A 5-membered monocyclic ring or a condensed ring of a 5-membered ring and a 6-membered ring is even more preferred.

The number of nitrogen atoms contained in the nitrogen-containing heterocyclic ring is preferably 1 to 4, and more preferably 2 to 4.

The nitrogen-containing heterocyclic ring may contain heteroatoms other than nitrogen atoms as ring members, but an embodiment in which the nitrogen-containing heterocyclic ring does not contain heteroatoms other than nitrogen atoms as ring members is also a preferred embodiment of the present invention. Examples of heteroatoms other than nitrogen atoms include oxygen atoms, sulfur atoms, and the like.

The nitrogen-containing heterocyclic ring may be an aliphatic ring or an aromatic ring, but an aromatic ring is preferred.

The specific nitrogen-containing compound may have two or more nitrogen-containing heterocyclic rings within its structure, but an embodiment in which the specific nitrogen-containing compound has only one nitrogen-containing heterocyclic ring is also a preferred embodiment of the present invention.

When the specific nitrogen-containing compound has two or more nitrogen-containing heterocyclic rings, it suffices that at least one of the nitrogen atoms serving as a ring member of at least one nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

From the perspective of long-term adhesion, the nitrogen-containing heterocyclic ring preferably comprises an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton. An imidazole ring, a triazole ring, a tetrazole ring, or a condensed ring of these rings with other rings is more preferred. A benzimidazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, or an adenine ring is even more preferred.

As the other ring, an aromatic ring is preferred, a 5-membered or 6-membered aromatic ring is more preferred, and a benzene ring is even more preferred.

[Amine]

Certain nitrogen-containing compounds contain amine groups.

One of the hydrogen atoms in the amino group can be substituted, but from the perspective of long-term bonding strength, it is preferred to leave it unsubstituted.

The substituent when one of the amino groups is substituted is not particularly limited and known substituents can be used. Examples include alkyl groups or groups containing at least one structure selected from the group consisting of -O-, -C(=O)-, -S- and -S(=O) ₂ - within the alkyl group.

The specific nitrogen-containing compound may have two or more amino groups, but having only one amino group is also one of the preferred aspects of the present invention.

Amine groups can be directly bonded to nitrogen-containing heterocyclic rings or through connecting chains.

As a connecting link, the base can be raised.

Among them, the aspect of direct bonding between the amino group and the nitrogen-containing heterocyclic ring is also one of the preferred aspects of the present invention.

The length of the linking chain between the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound and the nitrogen atom of the amine group is preferably 3 or less, more preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

In this specification, a "connecting chain" refers to the atomic chain connecting two atoms or groups of atoms in the path connecting the connecting targets in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, since there is one carbon atom in the shortest path, the length of the connecting chain between the amino group and the nitrogen atom contained in the triazole ring, which is a nitrogen-containing heterocyclic ring, is 1.

[Carbonyl, sulfonyl or thiocarbonyl]

In the specific nitrogen-containing compound, at least one nitrogen atom serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group.

Among these, in the specific nitrogen-containing compound, at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is preferably directly bonded to a carbonyl group or a sulfonyl group, and more preferably directly bonded to a carbonyl group.

From the perspective of long-term adhesion, it is preferred that the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the specific nitrogen-containing compound is directly bonded to the carbonyl group.

The specific nitrogen-containing compound may have two or more carbonyl groups, sulfonyl groups, or thiocarbonyl groups directly bonded to a nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring. However, an embodiment in which the specific nitrogen-containing compound has only one carbonyl group, sulfonyl group, or thiocarbonyl group directly bonded to a nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring is also a preferred embodiment of the present invention.

When the specific nitrogen-containing compound has two or more carbonyl groups, sulfonyl groups, or thiocarbonyl groups directly bonded to a nitrogen atom that is a ring member of a nitrogen-containing heterocyclic ring, the specific nitrogen-containing compound may have two or more groups selected from the group consisting of carbonyl groups, sulfonyl groups, and thiocarbonyl groups, or may have two or more groups selected from the group consisting of carbonyl groups, sulfonyl groups, and thiocarbonyl groups.

The group bonded to the side opposite to the nitrogen atom serving as a ring member of the nitrogen-containing heterocyclic ring in the carbonyl group, the sulfonyl group, or the thiocarbonyl group in the specific nitrogen-containing compound is not particularly limited, but examples thereof include a alkyl group or a group represented by a combination of a alkyl group and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -. A alkyl group is preferred.

Examples of the alkyl group include alkyl groups, alkenyl groups, and aryl groups. Preferred are alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, or aromatic alkyl groups having 6 to 20 carbon atoms. More preferred are alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and aromatic alkyl groups having 6 to 10 carbon atoms. These alkyl groups may further have substituents.

Specifically, examples include linear alkyl groups such as methyl, ethyl, and propyl; branched alkyl groups such as isopropyl, t-butyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentanyl, bornyl, isobornyl, and adamantyl; alkenyl groups such as methylvinyl; and aromatic hydrocarbon groups such as phenyl, naphthyl, 4-methylphenyl, and 2,6-methylphenyl.

The above-mentioned ^RN represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.

The group represented by a combination of a alkyl group and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N - is preferably a group represented by a combination of a alkyl group and at least one structure selected from the group consisting of -O- and -NR ^N -, and more preferably a group represented by the following formula (R-1) or (R-2).

In formula (R-1), R ^r1 represents a monovalent alkyl group, ^RN is as described above, and * represents a bonding site with the above-mentioned carbonyl group, the above-mentioned sulfonyl group, or the above-mentioned thiocarbonyl group.

In formula (R-2), R ^r2 represents a monovalent alkyl group, L ^r1 and L ^r2 each independently represent a divalent alkyl group, and * represents a bonding site to the carbonyl group, the sulfonyl group, or the thiocarbonyl group.

In formula (R-1), R ^r1 is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

In formula (R-2), R ^r2 is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

In formula (R-2), L ^r1 and L ^r2 are each independently preferably an alkylene group, more preferably an alkylene group having 2 to 10 carbon atoms, further preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an ethylene group or a propylene group.

[Formula (1-1) to Formula (3-1)]

Among these, the specific nitrogen-containing compound is preferably a compound represented by any one of the following formulas (1-1), (2-1), or (3-1).

In formula (1-1), ^R1 represents a monovalent organic group, ^R1a each independently represents a hydrogen atom or a substituent, and ^RN1 represents a hydrogen atom or a substituent; in formula (2-1), ^R2 represents a monovalent organic group, ^R2a represents a hydrogen atom or a substituent, and ^RN2 represents a hydrogen atom or a substituent; in formula (3-1), ^R3 represents a monovalent organic group, and ^RN3 represents a hydrogen atom or a substituent.

In formula (1-1), preferred embodiments of R ¹ are the same as those described above as the group bonded to the side opposite to the nitrogen atom that is a ring member of the nitrogen-containing heterocyclic ring, among the carbonyl group, the sulfonyl group, or the thiocarbonyl group.

In formula (1-1), R ^1a each independently represents a hydrogen atom or a substituent. Examples of substituents in R ^1a include alkyl groups, halogen atoms, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, and aryloxycarbonyl groups. Alkyl groups are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred. Among these, embodiments in which all R ^1a are hydrogen atoms or one or two of R ^1a are substituents are preferred.

In formula (1-1), ^RN1 represents a hydrogen atom or a substituent, preferably a hydrogen atom. Preferred embodiments of ^RN1 when it is a substituent are the same as those described above as substituents in the amino group.

In formula (1-2), R ² , R ^2a and ^RN2 have the same meanings as R ¹ , R ^1a and ^RN1 in formula (1-1), respectively, and preferred embodiments thereof are also the same.

In formula (1-3), R ³ and ^RN3 have the same meanings as R ¹ and ^RN1 in formula (1-1), respectively, and the preferred embodiments are also the same.

[Molecular weight]

From the perspective of adhesion over a long period of time, it is preferred that the molecular weight of the specific nitrogen-containing compound be less than 2000.

The lower limit of the molecular weight is preferably 120 or greater, and more preferably 150 or greater.

The upper limit of the molecular weight is preferably less than 1500, and even more preferably less than 1000.

As specific examples of specific nitrogen-containing compounds, the following compounds can be cited.

[Chemical formula 33]

(Synthesis Method)

The synthesis method of the specific nitrogen-containing compound is not particularly limited, but it can be obtained, for example, by reacting a nitrogen-containing heterocyclic compound having an amino group (one of the hydrogen atoms of the amino group may be substituted) with a carboxylic acid halide, a sulfonic acid halide, a thiocarboxylic acid halide, an isocyanate compound, or a thioisocyanate compound. Alternatively, it can be obtained by reacting a nitrogen-containing heterocyclic compound having an amino group with a carboxylic anhydride, or by condensing a nitrogen-containing heterocyclic compound having an amino group with a compound having an acid group such as a carboxylic acid group or a sulfonic acid group with an acid using a condensation agent such as carbodiimide.

The content of the specific nitrogen-containing compound is preferably 0.01 to 5.0 mass % relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 0.05 mass % or greater, and even more preferably 0.1 mass % or greater. The upper limit is more preferably 2.0 mass % or less, and even more preferably 1.0 mass % or less.

The specific nitrogen-containing compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

<Polymerizable Compound>

The resin composition of the present invention preferably contains a polymerizable compound.

Compounds corresponding to the above-mentioned specific nitrogen-containing compounds do not correspond to polymerizable compounds.

As polymerizable compounds, free radical crosslinking agents or other crosslinking agents can be cited.

[Free radical crosslinking agent]

The resin composition of the present invention preferably contains a free radical crosslinking agent.

A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferred free radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl, allyl, vinylphenyl, (meth)acryl, cis-butylenediimide, and (meth)acrylamide.

Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred as the group containing an ethylenically unsaturated bond. From the perspective of reactivity, (meth)acryl is more preferred.

Free radical crosslinkers are preferably compounds with one or more ethylenically unsaturated bonds, but compounds with two or more are even more preferred. Free radical crosslinkers may have three or more ethylenically unsaturated bonds.

As the compound having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred.

Furthermore, from the perspective of the film strength of the obtained pattern (cured product), it is also preferred that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the aforementioned compound having three or more ethylenically unsaturated bonds.

The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or greater.

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), or their esters and amides, preferably esters of unsaturated carboxylic acids with polyol compounds, and amides of unsaturated carboxylic acids with polyamine compounds. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group, an amino group, or a thiothio group with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, can also be preferably used. Also preferred are addition reaction products of unsaturated carboxylates or amides having electrophilic substituents such as isocyanate or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, as well as substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogen or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used in place of the unsaturated carboxylic acids. For specific examples, reference can be made to paragraphs 0113-0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference.

Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trihydroxymethylpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) Compounds obtained by acrylation, such as (meth)acrylic acid amine esters described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, multifunctional acrylates or methacrylates such as epoxy acrylates obtained as reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof, are also preferred. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Another example is a polyfunctional (meth)acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, with a polyfunctional carboxylic acid.

In addition to the above, preferred free radical crosslinking agents include compounds having a fluorene ring and two or more groups containing ethylenically unsaturated bonds, as described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, and cardo resins.

Other examples include the specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and the vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 02-025493. Furthermore, compounds containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan," vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these contents are incorporated into this specification.

Furthermore, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds described as formula (1) and formula (2) together with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then performing (meth)acrylic esterification.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

As free radical crosslinking agents, dipentatriol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.)) and structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

Examples of commercially available free radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethoxy chains, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, bifunctional methyl acrylates having four vinyloxy chains, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate having six pentoxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate having three isobutyloxy chains; amine oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300; and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF Corporation), etc.

Preferred free radical crosslinking agents include amine acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; and amine ester compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, as free radical crosslinking agents, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238, can also be used.

The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. Preferred free radical crosslinking agents having an acid group are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. More preferred are free radical crosslinking agents having an acid group formed by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound. Particularly preferred are free radical crosslinking agents having an acid group formed by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol. Commercially available products include polyacid-modified acrylic oligomers such as M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

The preferred acid value of a radical crosslinking agent containing an acid group is 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. A radical crosslinking agent with an acid value within this range provides excellent workability during production and, consequently, excellent developability. Furthermore, the polymerizability is good. The acid value is measured in accordance with JIS K 0070:1992.

From the perspective of pattern resolution and film stretchability, it is preferred to use a bifunctional methacrylate or acrylate as the resin composition.

As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, Alcohol dimethacrylate, dihydroxymethyltricyclodecane diacrylate, dihydroxymethyltricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with amine-ester bonds, bifunctional methacrylates with amine-ester bonds. Two or more of these may be used in combination as needed.

Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200.

Regarding the resin composition of the present invention, from the viewpoint of suppressing warping along with controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. Preferred monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives; N-vinyl pyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds; and alkenyl glycidyl ethers. Monofunctional radical crosslinking agents with a boiling point of 100°C or higher at normal pressure are also preferred to suppress volatility before exposure.

In addition, examples of bifunctional or higher-functional free radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a free radical crosslinking agent is present, its content is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the resin composition of the present invention. A lower limit of 5% by mass or greater is more preferred. An upper limit of 50% by mass or less is even more preferred, and 30% by mass or less is even more preferred.

Free radical crosslinking agents may be used alone or in combination. When using two or more, their combined amount is preferably within the above range.

[Other crosslinking agents]

The resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents.

In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. Compounds having multiple groups within their molecules that are activated by the above-mentioned photoacid generator or photoalkali generator to promote the formation of covalent bonds with other compounds in the composition or their reaction products are preferred. Compounds having multiple groups within their molecules that are activated by the action of an acid or base to promote the formation of covalent bonds with other compounds in the composition or their reaction products are preferred.

The acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator during the exposure step.

As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl is directly bonded to a nitrogen atom are more preferred.

Other crosslinking agents include compounds having a structure in which the hydrogen atoms of amino groups are substituted with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups by reacting formaldehyde or formaldehyde and alcohol with amino-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine. The production methods of these compounds are not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. Alternatively, oligomers formed by self-condensation of the hydroxymethyl groups of these compounds may be used.

Crosslinking agents using melamine as the amino-containing compound are called melamine-based crosslinking agents, crosslinking agents using glycoluril, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents.

Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of the glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

Examples of the compound containing at least one of the alkoxymethyl group and the acyloxymethyl group of the present invention include the alkoxymethyl group or the acyloxymethyl group being directly or trivalently attached to the aromatic group or the nitrogen atom of the following urea structure. The above-substituted compounds are used as structural examples.

The alkoxymethyl or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.

The total number of alkoxymethyl and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the above compound is preferably below 1500, preferably 180-1200.

R ₁₀₀ represents an alkyl group or an acyl group.

R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group directly substitutes an aromatic group include compounds of the following general formula.

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that is released by the action of an acid)).

R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less.

Examples of R ⁵ in the group that decomposes by the action of an acid to generate an alkali-soluble group, the group that is released by the action of an acid, and the group represented by -C(R ⁴ ) ₂ COOR ⁵ include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ).

In the formula, R ₃₆ to R ₃₉ independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to form a ring.

As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 5 carbon atoms is more preferred.

The above-mentioned alkyl group may be either linear or branched.

As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred.

The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.

The above-mentioned aryl group is preferably an aromatic alkyl group having 6 to 30 carbon atoms, and more preferably a phenyl group.

As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 16 carbon atoms is more preferred.

The above-mentioned aralkyl group refers to an aryl group substituted by an alkyl group. The preferred embodiments of the alkyl group and the aryl group are the same as the preferred embodiments of the above-mentioned alkyl group and the aryl group.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

Furthermore, these groups may have known substituents within the scope of achieving the effects of the present invention.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

Preferred groups that decompose with acid to generate alkaline-soluble groups or groups that are released with acid include tertiary alkyl ester groups, acetal groups, cumyl ester groups, and enol ester groups. Tertiary alkyl ester groups and acetal groups are more preferred.

Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds obtained by replacing the alkoxymethyl group in the following compounds with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited to these.

[Chemical formula 36]

[Chemical formula 37]

Compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group may be commercially available or synthesized by a known method.

From the viewpoint of heat resistance, the alkoxymethyl or acyloxymethyl group is directly Ring-substituted compounds are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, dimethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, dimethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoethoxymethylated glycoluril, monoethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoethoxymethylated glycoluril, trieth ... triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoethoxymethylated glycoluril, triethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycol Glycoluril-based crosslinking agents such as methylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, dipropoxymethyl urea, and dibutoxymethyl urea; Monohydroxymethylated ethylurea or dihydroxymethylated Ethylurea-based crosslinkers such as monomethoxymethylated ethylurea, dimethoxymethylated ethylurea, monoethoxymethylated ethylurea, diethoxymethylated ethylurea, monopropoxymethylated ethylurea, dipropoxymethylated ethylurea, monobutoxymethylated ethylurea, or dibutoxymethylated ethylurea; Propylene urea-based crosslinkers such as monohydroxymethylated propyleneurea, dihydroxymethylated propyleneurea, monomethoxymethylated propyleneurea, dimethoxymethylated propyleneurea, monoethoxymethylated propyleneurea, diethoxymethylated propyleneurea, monopropoxymethylated propyleneurea, dipropoxymethylated propyleneurea, monobutoxymethylated propyleneurea, or dibutoxymethylated propyleneurea; 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used.

Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Ketone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4"-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products may be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML- PE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, hereinafter the same) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

Furthermore, the resin composition of the present invention comprises a compound selected from epoxy compounds, cyclobutane oxide compounds and benzo It is also preferred that at least one compound in the group of compounds serves as another crosslinking agent.

-Epoxy compounds (compounds containing epoxy groups)-

Epoxy compounds preferably have two or more epoxy groups per molecule. Epoxy groups undergo crosslinking reactions at temperatures below 200°C and do not undergo dehydration reactions associated with crosslinking, thus less likely to cause film shrinkage. Therefore, the inclusion of epoxy compounds is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

Epoxy compounds preferably contain polyethylene oxide groups. This further reduces the elastic modulus and suppresses warping. A polyethylene oxide group refers to a group containing 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol epoxy resins or polyol hydrocarbon epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trihydroxymethylpropane triglycidyl ether; polyalkylene glycol epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy epoxy silicones such as polymethyl (glycidyloxypropyl) siloxane. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICL ON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, DIC CORPORATION), Rika Resin (Registered Trademark) BEO-20E, Rika Resin (Registered Trademark) BEO-60E, Rika Resin (Registered Trademark) HBE-100, Rika Resin (Registered Trademark) DME-100, Rika Resin (Registered Trademark) L-200 (Product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (The above are product names, ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all product names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds can also be preferably used.

[Chemical formula 38]

In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

In the above structure, from the perspective of balancing heat resistance and elongation, n is preferably 1-2 and m is preferably 3-7.

-Oxycyclobutane compounds (compounds containing an oxycyclobutane group)-

Examples of cyclooxetane compounds include compounds having two or more cyclooxetane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-cyclooxetane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)cyclooxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-cyclooxetane)methyl]ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used. These compounds can be used alone or in combination of two or more.

-Benzo Compounds (with benzo Azolyl compounds)-

Due to the cross-linking reaction caused by the ring-opening addition reaction, benzo Compounds that do not outgas during curing, thereby further reducing thermal shrinkage and inhibiting warping, are preferred.

As a benzo The best example of the compound is Pd-type benzo , Fa type benzo 、(the above are product names, made by Shikoku Chemicals Corporation), benzophenone of polyhydroxystyrene resin Adduct, novolac type dihydrobenzo These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1-30 mass% relative to the total solids content of the resin composition of the present invention, more preferably 0.1-20 mass%, even more preferably 0.5-15 mass%, and particularly preferably 1.0-10 mass%. The other crosslinking agent may be present in a single species or in two or more species. If two or more other crosslinking agents are present, their total content is preferably within the above range.

[Polymerization initiator]

The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferred that the resin composition contains a photopolymerization initiator.

The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are sensitive to light in the ultraviolet to visible range are preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active radicals may be used.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorbance of at least about 50 L/ ^mol⁻¹ / ^cm⁻¹ within a wavelength range of about 240-800 nm (preferably 330-500 nm). The molar absorbance of the compound can be measured using known methods. For example, it is preferably measured using a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photo-radical polymerization initiator, any known compound can be used. For example, halogenated hydrocarbon derivatives (such as those having three Skeleton compounds, with The present invention also includes compounds having a triazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, metallocene compounds, organoboron compounds, and iron aromatic complexes. For details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated herein by reference. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, Japanese Patent Application No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the peroxide-based photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in JP-A-2019-043864, the photopolymerization initiator described in JP-A-2019-044030, and the peroxide-based initiator described in JP-A-2019-167313, and the contents thereof are also incorporated into this specification.

Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, which is incorporated herein by reference. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and their contents are incorporated into this specification.

As α-hydroxyketone-based initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

As α-aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

As aminoacetophenone-based initiators, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm, can also be used, and this content is incorporated into this specification.

Examples of acylphosphine oxide-based initiators include 2,4,6-trimethylbenzyl-diphenylphosphine oxide. In addition, Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can also be used.

Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

Oxime compounds can be used as photoradical polymerization initiators to better catalyze the release of oximes. Using oxime compounds can more effectively improve exposure latitude. Oxime compounds are particularly advantageous because they have a wider exposure latitude (exposure margin) and also function as photohardening accelerators.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Unexamined Patent Application Publication No. 2004-534797, the compounds described in Japanese Unexamined Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent Application No. 6065596, the compounds described in International Publication No. 20 Compounds described in International Publication No. 2017/051680, compounds described in Japanese Patent Application Laid-Open No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and compounds described in International Publication No. 2013/167515 are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds having the following structures: 3-(benzyloxy(imino)butan-2-one, 3-(acetyloxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(imino))-1-phenylpropane-1-one, 2-(benzyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group >C=N-O-C(=O)- in the molecule.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, a photoradical polymerization initiator 2 described in JP-A-2012-014052) can also be preferably used. TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Alternatively, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Furthermore, oxime compounds having the following structures can also be used.

[Chemical formula 40]

Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and Japanese Patent No. 06636081, the contents of which are incorporated into this specification.

As a photoradical polymerization initiator, an oxime compound having a carbazole ring skeleton in which at least one benzene ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013/083505, the contents of which are incorporated into this specification.

Oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include the compounds described in Japanese Unexamined Patent Application Publication No. 2010-262028, compounds 24, 36, and 40 described in paragraph 0345 of Japanese Unexamined Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Application Publication No. 2013-164471. These details are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application No. 4223071, the contents of which are incorporated herein. Furthermore, an oxime compound having a nitro group can be exemplified by ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

Oxime compounds with a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

Oxime compounds in which a hydroxyl substituent is bonded to a carbazole skeleton can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019/088055, the contents of which are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having an aromatic ring group ^ArOX1 with an electron-withdrawing group introduced into the aromatic ring (hereinafter also referred to as the oxime compound OX) can also be used. Examples of the electron-withdrawing group possessed by the aromatic ring group ^ArOX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl groups and nitro groups are preferred. From the perspective of easily forming a film with excellent light resistance, acyl groups are more preferred, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclooxy group, an alkenyl group, an alkylthio group, an arylthio group, an acyl group, or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, an alkylthio group, an arylthio group, or an amino group is more preferred; and an alkoxy group, an alkylthio group, or an amino group is further preferred.

The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and the compound represented by formula (OX2) is more preferred.

wherein ^RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinyl group, a carbamoyl group, or a sulfonamido group,

^RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group,

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.

Among them, at least one of ^RX10 to ^RX14 is an electron-withdrawing group.

In the above formula, ^RX12 is an electron-withdrawing group, and ^RX10 , ^RX11 , ^RX13 , and ^RX14 are preferably hydrogen atoms.

Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated into this specification.

As the best oxime compounds, oxime compounds having specific substituents disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group disclosed in Japanese Patent Application Laid-Open No. 2009-191061 can be cited, and the contents thereof are incorporated into this specification.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is selected from the group consisting of trihalomethyl tri compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl Compounds from the group consisting of oxadiazole compounds and 3-aryl-substituted coumarin compounds are preferred.

A further preferred photo-radical polymerization initiator is trihalomethyl tris(2-hydroxy-2-nitropropene) Compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, selected from trihalomethyl tri More preferably, at least one compound selected from the group consisting of a compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is used, and even more preferably, a metallocene compound or an oxime compound is used.

Furthermore, photoradical polymerization initiators that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones formed by condensation of alkyl anthraquinones with aromatic rings, benzoin ether compounds such as benzoin alkyl ethers, benzoin and benzoin compounds such as alkyl benzoins, and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by the following formula (I) can also be used.

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group, or a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms; R ¹⁰¹ is a group represented by formula (II) or the same group as R ¹⁰⁰ ; and R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

wherein R ¹⁰⁵ to R ¹⁰⁷ are the same as R ¹⁰² to R ¹⁰⁴ in the above formula (I).

Furthermore, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as photoradical polymerization initiators, and such contents are incorporated into this specification.

Photoradical polymerization initiators with difunctional or trifunctional or higher functionality can be used. Using such initiators generates two or more free radicals per molecule, thereby achieving excellent sensitivity. Furthermore, using asymmetric compounds reduces crystallinity and improves solubility in solvents, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher-functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compounds (E) and (G) described in JP-A-2013-522445. ), Cmpd 1 to 7 described in International Publication No. 2016/034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Unexamined Patent Application No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Unexamined Patent Application No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent No. 6469669, and the contents thereof are incorporated into this specification.

When a photopolymerization initiator is included, its content is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, further preferably 0.5-15 mass%, and even more preferably 1.0-10 mass%, relative to the total solids content of the resin composition of the present invention. The photopolymerization initiator may be present in a single species or in two or more species. When two or more photopolymerization initiators are present, the total amount is preferably within the above range.

Furthermore, photopolymerization initiators sometimes also function as thermal polymerization initiators, so heating in an oven or hot plate can sometimes further promote crosslinking via the photopolymerization initiator.

[Sensitizer]

The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. This chemically decomposes the thermal radical polymerization initiator or the photoradical polymerization initiator, generating free radicals, acids, or bases.

As the sensitizer that can be used, benzophenone series, michler's ketone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxocyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenanthridine series, Series, pyrrolopyrazole azomethine series, Series, phthalocyanine series, benzopyran series, indigo series and other compounds.

Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino) Chalcone, p-dimethylaminophenylallylidene dihydroindanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone Aminobenzylidene) acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-benzylbenzimidazole, 1-phenyl-5-benzyltetrazole, 2-benzylbenzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, azole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc.

Alternatively, other sensitizing pigments may be used.

For details on sensitizing dyes, please refer to paragraphs 0161-0163 of Japanese Patent Application Laid-Open No. 2016-027357, which is incorporated into this manual.

When the resin composition contains a sensitizer, the sensitizer content is preferably 0.01-20 mass%, more preferably 0.1-15 mass%, and even more preferably 0.5-10 mass%, relative to the total solids content of the resin composition. Sensitizers may be used singly or in combination.

[Chain transfer agent]

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, _-SO2 -S-, -NO-, SH, PH, SiH, and GeH within the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds containing thiocarbonylthio groups useful for RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds generate free radicals by donating hydrogen to low-activity free radicals or by deprotonating after oxidation to generate free radicals. In particular, thiol compounds can be preferably used.

Furthermore, the compounds described in paragraphs 0152-0153 of International Publication No. 2015/199219 can also be used as chain transfer agents, and such contents are incorporated into this specification.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solids content of the resin composition of the present invention. The chain transfer agent may be a single type or two or more types. When two or more types of chain transfer agents are used, their total content is preferably within the above range.

[Photoacid generator]

The resin composition of the present invention preferably contains a photoacid generator.

A photoacid generator is a compound that generates at least one of a Brünster acid and a Lewis acid when irradiated with light in the range of 200 nm to 900 nm. The irradiated light preferably has a wavelength of 300 nm to 450 nm, more preferably 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator that generates an acid upon exposure is preferred.

Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonic acid amides.

Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, and onium salt compounds.

From the perspectives of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred. From the perspective of the mechanical properties of the formed film, oxime esters are preferred.

Examples of quinonediazide compounds include those obtained by bonding a sulfonic acid ester of quinonediazide to a monovalent or polyvalent hydroxyl compound, those obtained by bonding a sulfonic acid of quinonediazide to a monovalent or polyvalent amine compound via a sulfonamide, and those obtained by bonding a sulfonic acid of quinonediazide to a polyhydroxypolyamine compound via an ester bond and/or a sulfonamide. All functional groups in these polyhydroxy compounds, polyamine compounds, and polyhydroxypolyamine compounds may not be substituted with quinonediazide, but preferably, at least 40 mol% of the total functional groups are substituted with quinonediazide on average. By containing this quinone diazide compound, a resin composition can be obtained that is sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from mercury lamps, which are common ultraviolet rays.

Specific examples of the hydroxyl compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropyl alcohol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetri-FR-CR, BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are product names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (these are product names, manufactured by Asahi Yukizai Corporation), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but are not limited to these.

Specific examples of amino compounds include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl sulfide, but are not limited to these.

Furthermore, specific examples of polyhydroxypolyamino compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

Among these, quinone diazide compounds comprising phenolic compounds and esters with 4-naphthoquinone diazide sulfonyl groups are preferred. This allows for higher sensitivity and resolution to i-ray exposure.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. Setting the quinonediazide compound content within this range is preferred because it improves the contrast between exposed and unexposed areas, thereby achieving higher sensitivity. Furthermore, a sensitizer or the like may be added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also referred to as an "oxime sulfonate compound").

The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but oxime sulfonate compounds represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105) are preferred.

In formula (OS-1), ^X represents an alkyl group, an alkoxy group, or a halogen atom. When multiple ^Xs are present, they may be the same or different. The alkyl and alkoxy groups in ^X may have substituents. The alkyl group in ^X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in ^X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in ^X is preferably a chlorine atom or a fluorine atom.

In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plurality of ^X3 may be the same or different.

In formula (OS-1), ^R represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), the compound wherein m3 is 3, ^X3 is methyl, the substitution position of ^X3 is an ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorthomethyl, or p-tolyl is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, and the contents thereof are incorporated herein.

In Formulas (OS-103) to (OS-105), ^Rs1 represents an alkyl group, an aryl group, or a heteroaryl group; plural ^Rs2 groups may exist and each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom; plural ^Rs6 groups may exist and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer from 0 to 6.

In Formulas (OS-103) to (OS-105), the ^alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by Rs1 may have known substituents as long as the effects of the present invention can be achieved.

In Formulas (OS-103) to (OS-105), R ^<s2> is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. In a compound, where two or more R ^<s2> exist, one or two are preferably alkyl groups, aryl groups, or halogen atoms, more preferably one is an alkyl group, aryl group, or halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl or aryl group represented by ^R<s2> may have known substituents as long as the effects of the present invention are achieved.

In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, preferably O. In formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.

In Formula (OS-103) to Formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent.

In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110), or formula (OS-111). The compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107). The compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).

[Chemical formula 46]

In Formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group.

In formula (OS-106) to formula (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), ^Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. Preferably, it is an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group. More preferably, it is an alkyl group having 1 to 8 carbon atoms. Even more preferably, it is an alkyl group having 1 to 6 carbon atoms. Methyl is particularly preferred.

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom.

R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z) of the oxime may be any one or a mixture.

Specific examples of the oxime sulfonate compounds represented by Formula (OS-103) to Formula (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, and these contents are incorporated into this specification.

Other preferred embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. More preferably, R ^u9 is a cyano group or an aryl group. Even more preferably, R ^u9 is a cyano group, a phenyl group, or a naphthyl group.

In Formula (OS-101) or Formula (OS-102), R ^u2a represents an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, ^-NRu5- , _-CH2- , ^-CRu6H- , or ^CRu6Ru7- , and ^Ru5 to ^{Ru7 each} independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with the benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group, and at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, the embodiment in which all of R ^u1 to R ^u4 are hydrogen atoms is preferred. Each of the above substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).

Furthermore, in the above-mentioned oxime sulfonate compounds, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them or a mixture.

Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Laid-Open No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Laid-Open No. 2015-194674, and the contents thereof are incorporated into this specification.

Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

In addition, the compound represented by the following structural formula can also be cited as a preferred example.

Specific examples of organic halogenated compounds include Wakabayashi et al., Bull Chem. Soc Japan, 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Laid-Open No. 48-36281, Japanese Patent Application Laid-Open No. 55-32070, Japanese Patent Application Laid-Open No. 60-239736, Japanese Patent Application Laid-Open No. 61-169835, Japanese Patent Application Laid-Open No. 61-169837, Japanese Patent Application Laid-Open No. 62-58241, Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, and MP Hutt, "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970) and the like, and the contents thereof are incorporated into this specification. In particular, the compounds substituted with a trihalomethyl group can be cited. Azole compounds: S-triazole Compounds are preferred examples.

More preferably, at least one mono-, di- or tri-halogen substituted methyl group and s-tri- Ring key and get s-three Derivatives, specifically, include 2,4,6-tris(monochloromethyl)-s-tris 、2,4,6-tris(dichloromethyl)-s-tri 、2,4,6-tris(trichloromethyl)-s-tri , 2-methyl-4,6-bis(trichloromethyl)-s-tri , 2-n-propyl-4,6-bis(trichloromethyl)-s-tri 、2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tri , 2-phenyl-4,6-bis(trichloromethyl)-s-tri 、2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 、2-(3,4-Epoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 、2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri , 2-〔1-(p-methoxyphenyl)-2,4-butadienyl〕-4,6-bis(trichloromethyl)-s-tri , 2-phenylvinyl-4,6-bis(trichloromethyl)-s-tri 、2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri , 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-tri 、2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trimethylol 、2-(4-naphthyloxynaphthyl)-4,6-bis(trichloromethyl)-s-tri , 2-phenylthio-4,6-bis(trichloromethyl)-s-tri , 2-benzylthio-4,6-bis(trichloromethyl)-s-tri 、2,4,6-tris(dibromomethyl)-s-tri 、2,4,6-Tris(tribromomethyl)-s-tri , 2-methyl-4,6-bis(tribromomethyl)-s-tribromo , 2-methoxy-4,6-bis(tribromomethyl)-s-tri wait.

Examples of the organic borate compounds include Japanese Patent Application Laid-Open No. 62-143044, Japanese Patent Application Laid-Open No. 62-150242, Japanese Patent Application Laid-Open No. 9-188685, Japanese Patent Application Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz, Martin "Rad Tech '98. Proceedings April 19-22, 1998, Chicago" etc., organic borate salts described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561, organic boron-zirconia complexes or organic boron-oxygen-zirconia complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, organic boron-zirconia complexes described in Japanese Patent Laid-Open No. 6-175553 Specific examples include the organoboron phosphonium complexes described in Japanese Patent Application Laid-Open No. 9-188710, and organoboron transition metal complexes such as those disclosed in Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Application Laid-Open No. 7-128785, Japanese Patent Application Laid-Open No. 7-140589, Japanese Patent Application Laid-Open No. 7-306527, and Japanese Patent Application Laid-Open No. 7-292014, and the like, and their contents are incorporated into this specification.

Examples of disulfide compounds include compounds described in Japanese Patent Application Publication No. 61-166544, Japanese Patent Application Publication No. 2001-132318, and diazodisulfide compounds.

Examples of the onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. diazonium salts described in al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in U.S. Patent No. 4,069,055, U.S. Patent No. 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, iodonium salts described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 39 Copper salts described in the specifications of Patent No. 0,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V. Crivello et al, Macromolecules, 10(6), 1307(1977), J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047(1979), arsenic salts, pyridinium salts and other onium salts described in C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct(1988), and the contents thereof are incorporated into this specification.

Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III).

[Chemical formula 50]

In formula (RI-I), _Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms, an arylamide group having 6 to 20 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in each alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in each alkyl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, or an alkyl group, an alkenyl group, or an alkynyl group. Preferably, an aryl group is preferred from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

Specific examples of preferred photoacid generators include the following.

[Chemical formula 51]

[Chemical formula 52]

[Chemical formula 53]

[Chemical formula 54]

The photoacid generator concentration relative to the total solid content of the resin composition is preferably 0.1-20 mass%, more preferably 0.5-18 mass%, even more preferably 0.5-10 mass%, even more preferably 0.5-3 mass%, and even more preferably 0.5-1.2 mass%.

Photoacid generators can be used singly or in combination. When using multiple types in combination, the total amount is preferably within the above range.

In addition, in order to impart photosensitivity to the desired light source, it is also preferable to use it together with a sensitizer.

<Alkali Generator>

The resin composition of the present invention may contain an alkali generator. An alkali generator is a compound that can generate an alkali through physical or chemical reactions. Preferred alkali generators for the resin composition of the present invention include thermal alkali generators and photoalkali generators.

In particular, when the resin composition includes a precursor for a cyclized resin, it is preferable that the resin composition also include an alkali generator. By including a thermal alkali generator in the resin composition, the cyclization reaction of the precursor can be accelerated, for example, by heating, resulting in a cured product with improved mechanical properties and chemical resistance, such as interlayer insulation films for redistribution layers in semiconductor packages.

The base generator may be an ionic base generator or a non-ionic base generator. Examples of bases generated from the base generator include diamines and tertiary amines.

The base generator of the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include aminoformyl oxime compounds, aminoformylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonic acid amide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, o-xylylenediamine derivative compounds, and acyloxyimino compounds.

Specific examples of non-ionic base generators include compounds represented by formula (B1), formula (B2), or formula (B3).

In formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 cannot simultaneously be hydrogen atoms. Furthermore, ^Rb1 , ^Rb2 , and ^Rb3 do not have a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, even when the carbon atom to which the bond is formed is a carbonyl group, that is, when it forms an amide group together with the nitrogen atom, the structure is not limited thereto.

In formula (B1) and formula (B2), at least one of ^Rb1 , ^Rb2 , and ^Rb3 preferably comprises a cyclic structure, and at least two of them more preferably comprise a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), alkenyl groups (preferably having 2-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), aryl groups (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-10 carbon atoms), or aralkyl groups (preferably having 7-25 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). These groups may have substituents within the scope of the present invention. ^Rb1 and ^Rb2 may bond to each other to form a ring. The formed ring is preferably a 4-7 membered nitrogen-containing heterocyclic ring. In particular, ^Rb1 and ^Rb2 are preferably linear, branched, or cyclic alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, more preferably cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, and even more preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), An aralkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyloxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms). Among these, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkyloxy groups are preferred. ^Rb3 may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings as ^Rb1 and ^Rb2 in formula (B1), respectively.

^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), and may have a substituent within a range that allows the effects of the present invention to be exerted. Among them, ^Rb13 is preferably an aralkyl group.

^Rb33 and ^Rb34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), preferably an aryl group.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).

^Rb15 and ^Rb16 are hydrogen atom, alkyl group (preferably having 1-12 carbon atoms, more preferably 1-6 carbon atoms, and even more preferably 1-3 carbon atoms), alkenyl group (preferably having 2-12 carbon atoms, more preferably 2-6 carbon atoms, and even more preferably 2-3 carbon atoms), aryl group (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-10 carbon atoms), aralkyl group (preferably having 7-23 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-11 carbon atoms), preferably hydrogen atom or methyl group.

Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), wherein aryl is preferred.

In formula (B3), L represents an alkyl group, which is a divalent alkyl group having a saturated alkyl group along the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms along the linking chain is 3 or more. Furthermore, R ^N1 and R ^N2 each independently represent a monovalent organic group.

As mentioned above, in this specification, "connecting chain" refers to the shortest (smallest number of atoms) atomic chain connecting two atoms or groups of atoms in the path connecting the connecting targets. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, and has an ethylene group as a saturated alkyl group. The connecting chain consists of four carbon atoms, and the number of atoms in the connecting chain path (i.e., the number of atoms constituting the connecting chain, hereinafter also referred to as the "connecting chain length" or "chain length") is four.

[Chemical formula 60]

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the connecting chain) is preferably 3 to 24. The upper limit is 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or greater. From the perspective of rapid progress of the above-mentioned intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, with 4 being the most preferred. Specific preferred compounds as base generators include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002.

Furthermore, it is also preferred that the base generator contains a compound represented by the following formula (N1).

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking group preferably has a chain length of 1 or greater, more preferably 2 or greater. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length is the number of atoms in the atomic arrangement that forms the shortest distance between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), preferably a alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms), specifically, an aliphatic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms) or an aromatic alkyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), with aliphatic alkyl groups being preferred. Using an aliphatic alkyl group as R ^N1 and R ^N2 is preferred because the resulting base has a high basicity. Furthermore, the aliphatic alkyl group and the aromatic alkyl group may have a substituent, and the aliphatic alkyl group and the aromatic alkyl group may have an oxygen atom in the substituent in the aliphatic alkyl chain or in the aromatic ring. In particular, an embodiment in which the aliphatic alkyl group has an oxygen atom in the alkyl chain can be exemplified.

Examples of the aliphatic alkyl group constituting ^RN1 and ^RN2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, and isohexyl.

The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The group involved in the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group involved in the combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl.

Alkyl groups containing oxygen atoms in the chain preferably have 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. Alkyl groups containing oxygen atoms in the chain may be chain or cyclic, and may be straight or branched.

From the perspective of increasing the boiling point of the base generated by decomposition described later, ^RN1 and ^RN2 are preferably alkyl groups having 5 to 12 carbon atoms. In formulations where adhesion to metals (e.g., copper) during layering is important, groups having cyclic alkyl groups or alkyl groups having 1 to 8 carbon atoms are preferred.

^RN1 and ^RN2 can be linked to each other to form a ring structure. When forming a ring structure, an oxygen atom or the like can be contained in the chain. Furthermore, the ring structure formed by ^RN1 and ^RN2 can be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the ring structure formed, a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1) is preferred, for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidinyl ring, a pyrazolidinyl ring, a piperidine ... Ring, morpholine ring, etc., preferably pyrroline ring, pyrrolidinyl ring, piperidine ring, piperidine ring Ring, morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid can be exemplified as a preferred example.

Specific examples of protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain. Examples of chain or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of chain alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, epoxypropyl, cyclobutyl, tetrahydrofuryl, and tetrahydropyranyl (THP).

The divalent linking group constituting L is not particularly limited, but a alkyl group is preferred, and an aliphatic alkyl group is more preferred. The alkyl group may have a substituent and may have atoms other than carbon atoms in the alkyl chain. More specifically, a divalent alkyl linking group that may have an oxygen atom in the chain is preferred, a divalent aliphatic alkyl group that may have an oxygen atom in the chain, a divalent aromatic alkyl group, or a group related to a combination of a divalent aliphatic alkyl group that may have an oxygen atom in the chain and a divalent aromatic alkyl group that may have an oxygen atom in the chain is more preferred, and a divalent aliphatic alkyl group that may have an oxygen atom in the chain is even more preferred. These groups preferably do not have an oxygen atom.

The divalent alkyl linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic alkyl group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic alkyl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group associated with the combination of a divalent aliphatic alkyl group and a divalent aromatic alkyl group (e.g., an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

Specifically, the linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.

The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.

The group involved in the combination of chain alkylene groups and cyclic alkylene groups preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.

Alkylene groups with oxygen atoms in the chain can be chain- or cyclic-shaped, and can be straight or branched. Alkylene groups with oxygen atoms in the chain preferably have 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The linear or branched alkenylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2.

The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The arylene and alkylene groups preferably have 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.

Among them, chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, arylene groups, and alkylene groups are preferred. 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and oxyethylene (especially 1,2-vinyloxy-1,2-ethylene) are more preferred.

The following examples can be cited as alkali generators, but the present invention is not to be construed as being limited thereto.

[Chemical formula 62]

The molecular weight of the non-ionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds as ionic base generators include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited to them.

[Chemical formula 63]

As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited to them.

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or greater, and even more preferably 0.5 parts by mass or greater. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. It may be 5 parts by mass or less, or even 4 parts by mass or less.

Alkali generators can be used in combination of one or more types. When using two or more types, the total amount should preferably be within the above range.

<Solvent>

The resin composition of the present invention preferably contains a solvent.

Any known solvent can be used as the solvent. Preferably, the solvent is an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfones, amides, ureas, and alcohols.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), etc. esters, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

Preferred examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, and dihydroglucosanone.

Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfoxides, for example, dimethyl sulfoxide can be cited as a preferred one.

Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Preferred ureas include N,N,N’,N’-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methylphenyl carbinol, n-pentanol, methylpentanol, and diacetone alcohol.

Regarding solvents, mixing two or more solvents is preferred from the perspective of improving the properties of the coated surface.

In the present invention, one solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucosanone, and dihydroglucosanone, or a mixed solvent consisting of two or more of these is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the perspective of coating properties, the solvent content is preferably set so that the total solids concentration of the resin composition of the present invention is 5-80 mass%, more preferably 5-75 mass%, even more preferably 10-70 mass%, and even more preferably 20-70 mass%. The solvent content can be adjusted based on the desired coating thickness and coating method.

The resin composition of the present invention may contain only one solvent or two or more. When containing two or more solvents, it is preferred that the total amount of the solvents be within the above range.

<Metal Adhesion Improver>

The resin composition of the present invention preferably includes a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents containing alkoxysilyl groups, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds with sulfonamide structures, compounds with thiourea structures, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[Silane coupling agent]

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, and the compounds described in Japanese Patent Application Laid-Open No. 2014-191252. The compounds described in paragraphs 0060-0061 of JP-A-2014-041264, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, the compounds described in paragraph 0055 of JP-A-2014/097594, and the compounds described in paragraphs 0067-0078 of JP-A-2018-173573 are incorporated herein by reference, and the contents thereof are hereby incorporated herein by reference. Furthermore, as described in paragraphs 0050-0058 of JP-A-2011-128358, it is also preferred to use two or more different silane coupling agents. Furthermore, the following compounds are also preferred as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group.

[Chemical formula 65]

Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediaminetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based adhesive additive]

Examples of aluminum-based bonding agents include aluminum tris(ethyl acetate)aluminum, aluminum tris(acetylacetone), and aluminum diisopropyl acetate.

Furthermore, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. When the content is above the lower limit, the adhesion between the pattern and the metal layer is improved. When the content is below the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be used in a single or a combination of two or more. When two or more types are used, their combined content is preferably within the above range.

<Migration inhibitor>

The resin composition of the present invention may further contain a migration inhibitor.

Compounds corresponding to the above-mentioned specific nitrogen-containing compounds do not correspond to migration inhibitors.

By including a migration inhibitor, the migration of metal ions from the metal layer (metal wiring) into the film can be effectively suppressed.

Migration inhibitors are not particularly limited, but examples thereof include those having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, Azole, thiazole, pyrazole, iso Azole ring, isothiazole ring, tetrazole ring, pyridine ring, tantalum ring Ring, pyrimidine ring, pyridine Ring, piperidine ring, piperidine Ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri Compounds containing thioureas and thiohydrazides, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds are particularly preferred. Triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are particularly preferred.

Alternatively, an ion scavenger that captures anions such as halogen ions can be used.

Other migration inhibitors that can be used include the rustproofing agent described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015/199219. These contents are incorporated into this specification.

As specific examples of migration inhibitors, the following compounds can be cited.

[Chemical formula 66]

When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01-5.0 mass %, more preferably 0.05-2.0 mass %, and even more preferably 0.1-1.0 mass %, relative to the total solid content of the resin composition of the present invention.

The number of migration inhibitors may be one or more. If two or more migration inhibitors are used, their total amount is preferably within the above range.

<Polymerization Inhibitor>

The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

Specific examples of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first onium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, and ethylenediamine. Diaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy)- -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, phenothiazine ,coffee , 1,1-diphenyl-2-pyrrolohydrazide, dibutyl copper(II) dithiocarbonate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO-2015/125469 can also be used, and the contents thereof are incorporated into this specification.

When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition of the present invention.

The number of polymerization inhibitors may be one or more. When two or more polymerization inhibitors are used, their total amount is preferably within the above range.

<Acid scavenger>

To minimize performance changes over time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Acid scavengers are compounds that can capture generated acids by their presence in the system. Compounds with low acidity and high pKa are preferred. Preferred acid scavengers include compounds containing amine groups, with primary amines, diamines, tertiary amines, ammonium salts, and tertiary amides being preferred. Primary amines, diamines, tertiary amines, and ammonium salts are preferred, with diamines, tertiary amines, and ammonium salts being even more preferred.

Preferred examples of acid scavengers include compounds having an imidazole structure, a diazine bicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having hydroxyl and/or ether bonds, and aniline derivatives having hydroxyl and/or ether bonds. In the case of an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodonium, coronium, phosphonium, pyridinium, and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylcorbium hydroxide, benzylmethylcorbium hydroxide, and corbium hydroxides having a 2-oxoalkyl group, specifically triphenylcorbium hydroxide, tri(tert-butylphenyl)corbium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabiscycloundecane), DABCO (1,4-dimethylaniline), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, refined triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine , tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminopyrrolidine, aminoalkyl Phylin, etc.

These acid scavengers may be used alone or in combination of two or more.

The composition of the present invention may or may not contain an acid scavenger. However, if it does contain an acid scavenger, the content of the acid scavenger is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition.

The preferred ratio of acid generator to acid scavenger is 2.5 to 300 (molar ratio). Specifically, from the perspective of sensitivity and resolution, a molar ratio of 2.5 or greater is preferred, while from the perspective of suppressing the reduction in resolution caused by the thickening of the relief pattern over time after exposure and heat treatment, a molar ratio of 300 or less is preferred. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

<Other additives>

The resin composition of the present invention can be formulated with various additives as needed, within a range that achieves the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other additives (e.g., defoaming agents, flame retardants, etc.). By appropriately incorporating these ingredients, the physical properties of the film can be adjusted. For information on these ingredients, see, for example, paragraphs 0183 and thereafter of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101-0104 and 0107-0109 of Japanese Patent Application Publication No. 2008-250074, which are incorporated herein. When these additives are added, their total amount is preferably set to no more than 3% by mass of the solids content of the resin composition of the present invention.

[Surfactant]

As surfactants, various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, and the like. Surfactants can be non-ionic, cationic, or anionic.

By including a surfactant in the resin composition of the present invention, the liquid properties (particularly, fluidity) when preparing the coating liquid are further enhanced, thereby further improving coating thickness uniformity and liquid conservation. Specifically, when a film is formed using a coating liquid containing a composition containing a surfactant, the interfacial tension between the coating surface and the coating liquid is reduced, improving wettability to the coating surface and enhancing coating properties. Consequently, a uniform film with minimal thickness variations can be formed more effectively.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surf lon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (the above are manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (OMNOVA Solutions Inc.) etc. Fluorine-based surfactants may include compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 and in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503, and the contents of these compounds are incorporated herein. Block polymers may also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Application Laid-Open No. 2011-89090, and the contents of these compounds are incorporated herein.

Fluorine-based surfactants can also preferably be fluorine-containing polymers comprising repeating units derived from a (meth)acrylate compound having fluorine atoms and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably ethyleneoxy or propyleneoxy). The following compounds can also be exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000-50,000, more preferably 5,000-30,000.

Fluorine-based surfactants can also be made from fluorine-containing polymers having ethylenically unsaturated groups on their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Laid-Open No. 2010-164965, which are incorporated herein by reference. Commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in fluorine-based surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid conservation, and also have good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO., LTD.).

Examples of nonionic surfactants include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and their ethoxylates and propoxylates (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), OLFIN E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

A single surfactant may be used, or two or more surfactants may be used in combination.

The surfactant content is preferably 0.001-2.0 mass % relative to the total solid content of the composition, and more preferably 0.005-1.0 mass %.

[Higher fatty acid derivatives]

To prevent polymerization hindrance caused by oxygen, a higher fatty acid derivative such as behenic acid or behenyl amide may be added to the resin composition of the present invention so that it is unevenly distributed on the surface of the resin composition during the drying process after coating.

Furthermore, higher fatty acid derivatives may also include the compounds described in paragraph 0155 of International Publication No. 2015/199219, and such content is incorporated into this specification.

When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition of the present invention. The higher fatty acid derivative may be a single type or two or more types. When two or more types are present, their total content is preferably within the above range.

[Thermal polymerization initiator]

The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals using thermal energy, initiating or accelerating the polymerization reaction of a polymerizable compound. The addition of a thermal free radical polymerization initiator enables the polymerization reaction of the resin and the polymerizable compound to proceed, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator may also function to initiate polymerization using heat and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554, the contents of which are incorporated into this specification.

When a thermal polymerization initiator is included, its content is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, and even more preferably 0.5-15 mass%, relative to the total solids content of the resin composition of the present invention. A single thermal polymerization initiator may be included, or two or more may be included. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[Inorganic particles]

The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

The average particle size of the inorganic particles is preferably 0.01-2.0 μm, more preferably 0.02-1.5 μm, even more preferably 0.03-1.0 μm, and particularly preferably 0.04-0.5 μm.

The above average particle size of the inorganic particles is the primary particle size and the volume average particle size. The volume average particle size can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

When the above measurements are difficult to perform, measurements can also be performed using centrifugal sedimentation transmission method, X-ray transmission method, and laser diffraction/scattering method.

[UV absorber]

The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris-based It is an ultraviolet absorber.

Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based UV absorbers include 2-cyano-3,3-diphenyl ethyl acrylate and 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate. Examples of ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazol-2-yl ... , 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tridecyl , 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Mono(hydroxyphenyl)tris(hydroxyphenyl) Compound; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine , 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine 、2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris Compound; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris( ... , 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(2-hydroxy-4-octyloxyphenyl) , 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris Tris(hydroxyphenyl)tris Compounds, etc.

In the present invention, the above-mentioned UV absorbers may be used alone or in combination of two or more.

The composition of the present invention may or may not contain a UV absorber. However, if included, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, relative to the total solids content of the composition of the present invention.

[Organic titanium compounds]

The resin composition of this embodiment may contain an organic titanium compound. Because the resin composition contains an organic titanium compound, it is possible to form a resin layer with excellent chemical resistance even when curing at low temperatures.

As usable organic titanium compounds, those in which organic groups are bonded to titanium atoms via covalent bonds or ionic bonds can be cited.

Specific examples of organic titanium compounds are shown in the following I) to VII):

I) Titanium chelate compounds: Titanium chelate compounds with two or more alkoxy groups are preferred, as they provide excellent storage stability of the resin composition and can produce a good hardening pattern. Specific examples include titanium diisopropyl bis(triethanolamine), titanium di(n-butanol)bis(2,4-pentanedione), titanium diisopropyl bis(2,4-pentanedione), titanium diisopropyl bis(tetramethylheptanedione), and titanium diisopropyl bis(ethyl acetylacetate).

II) Tetraalkoxytitanium compounds: Examples include titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethanol, titanium tetramethoxypropanol, titanium tetramethylphenoxide, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, and titanium tetra[bis{2,2-(allyloxymethyl)butanol}].

III) Titanium cyclopentadienyl compounds: Examples include titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

IV) Monoalkoxy titanium compounds: Examples include titanium tris(dioctyl phosphate) isopropylate and titanium tris(dodecylphenyl sulfonate) isopropylate.

V) Titanium oxide compounds: for example, titanium bis(pentanedione) oxide, titanium bis(tetramethylheptanedione) oxide, titanium phthalocyanine oxide, etc.

VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate.

VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium salt, etc.

Among these, the organic titanium compound is preferably selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titaniumocene compounds, from the perspective of exhibiting better chemical resistance. In particular, titanium bis(ethyl acetylacetate)diisopropylate, titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the preferred amount is 0.05-10 parts by mass, and more preferably 0.1-2 parts by mass, per 100 parts by mass of the specific resin. Amounts of 0.05 parts by mass or greater effectively exhibit excellent heat and chemical resistance in the resulting cured pattern. On the other hand, a compounding amount of 10 parts by mass or less provides superior storage stability.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the elongation properties and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position) are preferred. Preferred substituents are substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenolic group and a phosphite group in the same molecule. Furthermore, phosphorus-based antioxidants are also preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and this disclosure is incorporated herein. Furthermore, the composition of the present invention may contain a potential antioxidant, if desired. Potential antioxidants include compounds in which the site that exerts antioxidant activity is protected by a protecting group, and compounds that exert antioxidant activity by removing the protecting group when heated at 100-250°C or at 80-200°C in the presence of an acid/base catalyst. Potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and JP-A-2017-008219, the contents of which are incorporated herein. Commercially available products that are potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).

As examples of preferred antioxidants, there are 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and the compound represented by formula (3).

[Chemical formula 68]

In general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R7 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or a monovalent to tetravalent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer of 1 to 4.

The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups in the resin. It can also inhibit metal oxidation by providing a rust-proofing effect on metal materials.

Because it can act simultaneously on both the resin and the metal material, k is preferably an integer of 2 to 4. Examples of R ⁷ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof. The group may further have a substituent. From the perspectives of solubility in developer solutions and metal adhesion, alkyl ether groups and -NH- are preferred. From the perspectives of interaction with the resin and metal adhesion during metal complex formation, -NH- is more preferred.

Regarding the compounds represented by general formula (3), the following can be cited as examples, but they are not limited to the following structures.

[Chemical formula 69]

[Chemical formula 70]

[Chemical formula 71]

[Chemical formula 72]

The antioxidant addition amount is preferably 0.1-10 parts by weight relative to the resin, and more preferably 0.5-5 parts by weight. An addition amount of 0.1 parts by weight or greater improves elongation and adhesion to metals, even in high-temperature and high-humidity environments. An addition amount of 10 parts by weight or less enhances the sensitivity of the resin composition, for example, through interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

[Anti-agglomerant]

The resin composition of this embodiment may contain an anti-agglomerating agent as needed. Examples of such anti-agglomerating agents include sodium polyacrylate.

In the present invention, the anti-agglomerating agent may be used alone or in combination of two or more.

The composition of the present invention may or may not contain an anti-aggregating agent. However, if included, the content of the anti-aggregating agent is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, relative to the total solids content of the composition of the present invention.

[Phenolic compounds]

The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, and BisRS-26X (all product names, manufactured by Honshu Chemical Industry Co., Ltd.), and BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all product names, manufactured by Asahi Yukizai Corporation).

In the present invention, the phenolic compound may be used alone or in combination of two or more.

The composition of the present invention may or may not contain a phenolic compound. However, if a phenolic compound is contained, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solid content of the composition of the present invention.

[Other polymer compounds]

Examples of other polymers include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymers may be modified products in which crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

In the present invention, other polymer compounds may be used alone or in combination of two or more.

The composition of the present invention may or may not contain other polymer compounds. However, if included, the content of the other polymer compounds is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solid content of the composition of the present invention.

<Characteristics of Resin Composition>

The viscosity of the resin composition of the present invention can be adjusted by adjusting the solids concentration of the resin composition. From the perspective of coating film thickness, a viscosity of 1,000 ^mm² /s to 12,000 ^mm² /s is preferred, 2,000 ^mm² /s to 10,000 ^mm² /s is more preferred, and 2,500 ^mm² /s to 8,000 ^mm² /s is even more preferred. Within this range, a highly uniform coating film is easily obtained. When the speed is 1,000 mm ² /s or higher, for example, coating with the required film thickness for redistribution wiring insulation is easy, and when the speed is 12,000 mm ² /s or lower, a coating with excellent surface morphology can be obtained.

<Regarding restrictions on substances contained in resin compositions>

The resin composition of the present invention preferably has a moisture content of less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. A moisture content of less than 2.0% improves the storage stability of the resin composition.

Methods for maintaining moisture content include adjusting the humidity during storage and reducing the porosity of the storage container.

From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals contained in the form of complexes of organic compounds and metals. If multiple metals are contained, the total content of these metals is preferably within the above range.

Furthermore, as methods for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as the raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention through a filter; and lining the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination.

Considering the use of the resin composition of the present invention as a semiconductor material, from the perspective of wiring corrosion resistance, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. In particular, the halogen ion content is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferred that the total content of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned ranges.

As a method for adjusting the halogen atom content, ion exchange treatment can be preferably cited.

Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to prevent contamination of the raw materials or the resin composition of the present invention, it is also preferable to use a multilayer bottle with an inner wall composed of six layers of six different resins, or a bottle with a seven-layer structure composed of six different resins. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

<Hardened resin composition>

By hardening the resin composition of the present invention, a hardened product of the resin composition can be obtained.

The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

The resin composition is preferably cured by heating, with the heating temperature preferably being in the range of 120°C to 400°C, more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured resin composition is not particularly limited and can be selected from a film, rod, sphere, or granular shape depending on the intended use. In the present invention, a film-like shape is preferred. Furthermore, by patterning the resin composition, the shape of the cured product can be selected to suit various applications, such as forming a protective film on the wall, forming a hole (beer hall) for conduction, adjusting impedance or electrostatic capacitance, or internal stress, or imparting heat dissipation. The thickness of the cured product (film formed by the cured product) is preferably not less than 0.5 μm and not more than 150 μm.

The resin composition of the present invention preferably exhibits a shrinkage rate of 50% or less during curing, more preferably 45% or less, and even more preferably 40% or less. The shrinkage rate refers to the percentage change in volume of the resin composition before and after curing and can be calculated using the following formula.

Shrinkage rate [%] = 100 - (volume after hardening ÷ volume before hardening) × 100

<Characteristics of Cured Resin Compositions>

The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. A rate of 70% or higher can sometimes produce a cured product with excellent mechanical properties.

The cured resin composition of the present invention preferably has an elongation at break of 30% or greater, more preferably 40% or greater, and even more preferably 50% or greater.

The cured resin composition of the present invention preferably has a glass transition temperature (Tg) of 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of resin composition>

The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out by conventionally known methods.

Mixing can be performed using a stirring blade, a ball mill, or a rotating tank.

The mixing temperature is preferably 10-30°C, and more preferably 15-25°C.

Furthermore, in order to remove foreign matter such as dust or particles from the resin composition of the present invention, it is preferred to filter the resin composition using a filter. Regarding the pore size of the filter, for example, 5 μm or less can be cited, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. In the case where the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtering step, multiple filters can also be connected in series or in parallel. When using multiple filters, filters of different pore sizes or materials can be combined. For example, a 1μm HDPE filter can be connected in series as the first stage, followed by a 0.2μm HDPE filter as the second stage. Furthermore, various materials can be filtered multiple times. This multiple-pass filtering process can be cycled. Furthermore, filtration can be performed under pressure. When filtration is performed under pressure, the pressure can be, for example, 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa.

In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filtering and impurity removal using an adsorbent can also be combined. Known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

Furthermore, after filtering using a filter, the resin composition filled in the bottle may be placed under reduced pressure to degas.

(Method for producing hardened material)

The method for producing the cured product of the present invention preferably includes a film-forming step of applying the resin composition to a substrate to form a film.

Furthermore, the method for producing a cured product of the present invention preferably includes the aforementioned film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern.

The method for producing a cured product of the present invention particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.

Furthermore, the manufacturing method of the present invention preferably includes the above-mentioned film forming step and the step of heating the above-mentioned film.

The following describes the details of each step.

<Membrane Formation Step>

The resin composition of the present invention can be used in a film-forming step for forming a film on a substrate.

The method for producing the cured product of the present invention preferably includes a film-forming step of applying the resin composition to a substrate to form a film.

[Base material]

The type of substrate can be appropriately selected depending on the intended use, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., either a substrate formed of metal or a substrate having a metal layer formed by electroplating or evaporation); paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDPs). In the present invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred.

Furthermore, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate.

Furthermore, the shape of the substrate is not particularly limited and can be circular or rectangular.

The dimensions of the substrate are, for example, a circular substrate with a diameter of 100-450 mm, preferably 200-450 mm. For a rectangular substrate, the length of the short side is, for example, 100-1000 mm, preferably 200-700 mm.

Furthermore, as the base material, for example, a plate-shaped base material (substrate) can be used, preferably a panel-shaped base material (substrate).

Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

Specific examples of applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet coating. From the perspective of film thickness uniformity, spin coating, slit coating, spray coating, or ink jet coating is more preferred. From the perspective of film thickness uniformity and productivity, spin coating and slit coating are particularly preferred. By adjusting the solid content concentration of the resin composition and coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected based on the substrate shape. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. For spin coating, for example, a rotation speed of 500 to 3,500 rpm can be used for approximately 10 seconds to 3 minutes.

Furthermore, a method of transferring a coating film formed by pre-applying the above-mentioned applying method to a dummy support onto a substrate can also be applied.

Regarding the transfer method, the present invention can also preferably use the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592.

Furthermore, a step may be performed to remove excess film from the edges of the substrate. Examples of such steps include edge bead rinsing (EBR) and back rinse.

Alternatively, a pre-wetting step may be employed. Before applying the resin composition onto the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying Steps>

After the film formation step (layer formation step), the film may be subjected to a drying step (drying step) to remove the solvent.

That is, the method for producing a cured product of the present invention may include a drying step for drying the film formed in the film forming step.

Furthermore, the drying step is preferably performed after the film forming step and before the exposure step.

The film is preferably dried at a temperature of 50-150°C during the drying step, more preferably 70-130°C, and even more preferably 90-110°C. Drying can also be performed by reducing pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1-10 minutes, and even more preferably 2-7 minutes.

<Exposure Steps>

The above film can be used in an exposure step for selectively exposing the film.

That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step.

Selective exposure means exposing a portion of a film to light. Furthermore, selective exposure forms exposed areas (exposed portions) and unexposed areas (non-exposed portions) on the film.

There are no particular restrictions on the exposure dose as long as it can cure the resin composition of the present invention. For example, an exposure energy of 50 to 10,000 mJ/cm ² at a wavelength of 365 nm is preferably, and 200 to 8,000 mJ/cm ² is more preferably.

The exposure wavelength can be appropriately set within the range of 190-1,000nm, with 240-550nm being optimal.

Regarding the exposure wavelength, if we explain it in terms of its relationship with the light source, we can cite (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet ray; EUV (wavelength 13.6nm), (6) electron beam, (7) second harmonic 532nm and third harmonic 355nm of YAG laser, etc. With regard to the resin composition of the present invention, exposure based on a high pressure mercury lamp is particularly preferred, and exposure based on i-ray is particularly preferred. This allows for exceptionally high exposure sensitivity.

The exposure method is not particularly limited, as long as it is a method that exposes at least a portion of the film formed from the resin composition of the present invention. Examples include exposure using a photomask and exposure based on laser direct imaging.

<Post-exposure heating step>

The above film may be subjected to a step of heating after exposure (post-exposure heating step).

That is, the method for producing a cured product of the present invention may include a post-exposure heating step, wherein the post-exposure heating step heats the film exposed in the exposure step.

The post-exposure heating step can be performed after the exposure step and before the development step.

The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C.

The optimal heating time during the post-exposure heating step is 30 seconds to 300 minutes, and even more preferably 1 minute to 10 minutes.

Regarding the heating rate during the post-exposure heating step, a heating rate of 1-12°C/minute from the initial heating temperature to the maximum heating temperature is preferred, 2-10°C/minute is more preferred, and 3-10°C/minute is even more preferred.

In addition, the heating rate can be appropriately changed during the heating process.

The heating mechanism used in the post-exposure heating step is not particularly limited, and a known heating plate, oven, infrared heater, etc. can be used.

Furthermore, it is also preferable to perform the process in an environment with low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon during heating.

<Development Steps>

After exposure, the film can be subjected to a developing step in which a developer is used to form a pattern.

That is, the method for producing a cured product of the present invention may include a developing step in which a developer is used to develop the film exposed in the exposing step to form a pattern. The development step removes one of the exposed and unexposed portions of the film, thereby forming a pattern.

Among them, developing the non-exposed areas of the film after removal by the developing step is called negative development, and developing the exposed areas of the film after removal by the developing step is called positive development.

[Developer]

As the developer used in the developing step, an alkaline aqueous solution or a developer containing an organic solvent can be cited.

In the case where the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (Tetrapropylammonium hydroxide), Hydroxide), tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. For example, when using TMAH, the content of the alkaline compound in the developer is preferably 0.01-10 mass %, more preferably 0.1-5 mass %, and even more preferably 0.3-3 mass % of the total mass of the developer.

When the developer contains an organic solvent, the organic solvent may preferably be ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3- Methyl alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and Ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Sulfides include, for example, dimethyl sulfoxide. Alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, one organic solvent or a mixture of two or more organic solvents can be used. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred. A developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is even more preferred. A developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent is preferably 50% by mass or greater, more preferably 70% by mass or greater, even more preferably 80% by mass or greater, and particularly preferably 90% by mass or greater, relative to the total mass of the developer. Alternatively, the above content may be 100% by mass.

The developer may further contain other ingredients.

Other ingredients include, for example, well-known surfactants and well-known defoaming agents.

[Developer Supply Method]

There are no particular restrictions on the method for supplying the developer solution, as long as the desired pattern can be formed. Examples include immersing the film-formed substrate in the developer solution, using a nozzle to supply the developer solution to the film formed on the substrate for immersion development, and continuously supplying the developer solution. The type of nozzle is not particularly limited, and examples include vertical nozzles, shower nozzles, and mist nozzles.

From the perspectives of developer permeability, removal of non-image areas, and manufacturing efficiency, a method using a vertical nozzle to supply developer or a method using a mist nozzle for continuous supply is preferred. From the perspective of developer permeability to the image area, a method using a mist nozzle for supply is even more preferred.

Alternatively, a process may be employed in which the developer is continuously supplied using a vertical nozzle, the substrate is rotated to remove the developer, and after drying by rotation, the developer is continuously supplied again using the vertical nozzle, and the substrate is rotated to remove the developer. This process may be repeated multiple times.

Furthermore, as a method for supplying the developer solution during the development step, a step of continuously supplying the developer solution to the substrate, a step of maintaining the developer solution substantially stationary on the substrate, a step of vibrating the developer solution on the substrate using ultrasound or the like, or a combination of these steps can be employed.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no specific requirement for the developer temperature during development, but it can be performed at a temperature between 10°C and 45°C, and more preferably between 18°C and 30°C.

In the development step, after treatment with a developer, the pattern can be further cleaned (rinsed) with a rinse solution. Alternatively, a method can be employed in which the rinse solution is supplied before the developer in contact with the pattern has completely dried.

[Rinse fluid]

When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse liquid. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

When the rinsing liquid contains an organic solvent, the organic solvent includes, for example, esters, preferably ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxy Methyl propionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like; and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and as ketones, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like are preferably mentioned. Preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Preferred examples include cyclic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred examples include sulfoxides such as dimethyl sulfoxide. Preferred examples include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred examples include amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinse solution contains an organic solvent, one organic solvent or a mixture of two or more organic solvents may be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being even more preferred, and cyclohexanone and PGMEA being even more preferred.

When the rinse liquid contains an organic solvent, it is preferably 50% by mass or more of the rinse liquid, more preferably 70% by mass or more of the rinse liquid, and even more preferably 90% by mass or more of the rinse liquid. Alternatively, the rinse liquid may comprise 100% by mass of the organic solvent.

The rinse may further comprise other ingredients.

Other ingredients include, for example, well-known surfactants and well-known defoaming agents.

[How to supply flushing fluid]

There are no particular restrictions on the method for supplying the rinse liquid, as long as the desired pattern can be formed. Examples include immersing the substrate in the rinse liquid, performing immersion development on the substrate, spraying the rinse liquid onto the substrate, and continuously supplying the developer liquid to the substrate using a mechanism such as a vertical nozzle.

From the perspectives of rinse liquid permeability, removal of non-image areas, and manufacturing efficiency, there are various methods for supplying rinse liquid using shower nozzles, vertical nozzles, and mist nozzles. Continuous supply using a mist nozzle is preferred, and from the perspective of rinse liquid permeability into the image area, supply using a mist nozzle is even more preferred. The type of nozzle is not particularly limited, and examples include vertical nozzles, shower nozzles, and mist nozzles.

That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a vertical nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle.

Furthermore, as a method for supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of maintaining the rinsing liquid substantially stationary on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, or a combination of these steps can be employed.

The optimal rinsing time is 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinse solution is not particularly specified, but it can be performed at a temperature between 10°C and 45°C, and more preferably between 18°C and 30°C.

<Heating Steps>

The pattern obtained by the development step (or the pattern after development if a development step is performed) can be subjected to a heating step for heating the pattern obtained by the development step.

That is, the method for manufacturing a cured product of the present invention may include a heating step, wherein the heating step heats the pattern obtained by the development step.

Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by other methods without performing a development step, or a film obtained by a film forming step.

During the heating step, the polyimide precursor and other resins are cyclized to form polyimide and other resins.

In addition, it also crosslinks unreacted crosslinking groups in the specific resin or crosslinking agents other than the specific resin.

The heating temperature (maximum heating temperature) in the heating step is preferably 50-450°C, more preferably 150-350°C, even more preferably 150-250°C, even more preferably 160-250°C, and particularly preferably 160-230°C.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and utilizing the action of the base generated from the base generator.

During the heating step, the heating process should be performed at a rate of 1-12°C/minute from the initial heating temperature to the maximum heating temperature. A rate of 2-10°C/minute is more preferred, and 3-10°C/minute is even more preferred. A rate of 1°C/minute or higher ensures productivity while preventing excessive volatilization of the acid or solvent. A rate of 12°C/minute or lower alleviates residual stress in the cured product.

In addition, in the case of an oven capable of rapid heating, a heating rate of 1-8°C/second from the initial heating temperature to the maximum heating temperature is preferred, 2-7°C/second is more preferred, and 3-6°C/second is even more preferred.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, this refers to the temperature of the dried film (layer). For example, it is preferred to start heating at a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

The optimal heating time (heating time at the highest heating temperature) is 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming a multi-layer laminate, from the perspective of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C/minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C/minute and holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, treatment while irradiating with UV light is also preferred. This pretreatment step can improve membrane properties. The pretreatment step can be performed for a short period of time, from about 10 seconds to 2 hours, preferably from 15 seconds to 30 minutes. Pretreatment can be performed in two or more stages. For example, the first stage of pretreatment can be performed at a temperature between 100 and 150°C, followed by a second stage of pretreatment at a temperature between 150 and 200°C.

Furthermore, cooling can be performed after heating. The optimal cooling rate is 1-5°C/minute.

To prevent the decomposition of certain resins, it is best to perform the heating process in a low-oxygen environment, such as by flowing an inert gas such as nitrogen, helium, or argon during the heating step and performing the process under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred.

The heating mechanism in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven, etc.

<Post-development exposure step>

Instead of or in addition to the aforementioned heating step, the pattern obtained by the development step (the pattern after development if a development step is performed) may be used in the post-development exposure step of the pattern after the development step.

That is, the method for producing a cured product of the present invention may include a post-development exposure step, in which the pattern obtained by the development step is exposed. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.

In the post-development exposure step, for example, the cyclization reaction of a polyimide precursor can be promoted by sensitization with a photoalkali generator, or the elimination reaction of an acid-degradable group can be promoted by sensitization with a photoacid generator.

In the post-development exposure step, it is sufficient to expose at least a portion of the pattern obtained in the development step, but it is preferably to expose the entire pattern.

The exposure dose in the post-development exposure step is preferably 50-20,000 mJ/cm ² , more preferably 100-15,000 mJ/cm ² , calculated as exposure energy at a wavelength to which the photosensitive compound is sensitive.

The post-development exposure step can be performed using the light source used in the above-mentioned exposure step, preferably broadband light.

<Metal layer formation step>

The pattern obtained by the development step (preferably the pattern used in at least one of the heating step and the post-development exposure step) can be used in the metal layer formation step of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step, wherein the metal layer is formed on a pattern obtained by the development step (preferably a pattern provided for at least one of a heating step and a post-development exposure step).

The metal layer is not particularly limited, and existing metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese National Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, U.S. Patent No. 7,888,181B2, and U.S. Patent No. 9,177,926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be used. More specifically, patterning methods that combine sputtering, photolithography, and etching, and those that combine photolithography and electrolytic plating can be cited. Preferred examples of electroplating include electrolytic plating using copper sulfate or copper cyanide plating solutions.

The thickness of the metal layer is preferably 0.01-50μm at the thickest part, and more preferably 1-10μm.

<Purpose>

Examples of fields in which the method for producing a cured article of the present invention or the cured article of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. Other examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and situations in which patterns are formed by etching insulating films for practical mounting applications such as those described above. For information on these applications, see, for example, "Advanced Functionality and Application Technology of Polyimides" by Science & Technology Co., Ltd., April 2008; "Fundamentals and Development of Polyimide Materials" by Masaaki Kakimoto, CMC Technical Library, November 2011; and "Latest Polyimide Fundamentals and Applications" by the Japan Polyimide/Aromatic Polymer Research Society, NTS, August 2010.

Furthermore, the method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates, screen printing plates, and other printing surfaces, in the production of etched components, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

(Laminar body and method for manufacturing the same)

The laminate of the present invention refers to a structure having multiple layers formed from the cured product of the present invention.

The laminate of the present invention is a laminate comprising two or more layers formed of a cured material, and may also be a laminate comprising three or more layers.

At least one of the two or more layers formed of the cured material included in the laminate is a layer formed of the cured material of the present invention. From the perspective of suppressing shrinkage of the cured material or deformation of the cured material associated with such shrinkage, it is also preferred that all layers formed of the cured material included in the laminate be layers formed of the cured material of the present invention.

That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened product of the present invention, and more preferably includes repeating the steps of the method for manufacturing the laminate of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers formed of a hardened material, and preferably includes a metal layer between any of the layers formed of the hardened material. The metal layer is preferably formed by the metal layer forming step described above.

That is, the laminate manufacturing method of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer formed from the hardened product between the multiple steps of manufacturing the hardened product. The preferred embodiment of the metal layer forming step is as described above.

As the aforementioned laminate, a laminate having a layered structure including at least three layers stacked in sequence: a first layer formed of a hardened material, a metal layer, and a second layer formed of a hardened material can be cited as a preferred example.

It is preferred that both the first layer formed of the cured product and the second layer formed of the cured product be layers formed of the cured product of the present invention. The resin composition of the present invention used to form the first layer formed of the cured product and the resin composition of the present invention used to form the second layer formed of the cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

<Layering steps>

The method for manufacturing the laminate of the present invention preferably includes a lamination step.

The lamination step comprises a series of steps comprising, on the surface of the pattern (resin layer) or metal layer, performing again, in order, (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and at least one of a post-development exposure step. Alternatively, (a) the film formation step and (d) the heating step and at least one of the post-development exposure step may be repeated. Furthermore, (e) a metal layer formation step may be further included after at least one of (d) the heating step and the post-development exposure step. It goes without saying that the lamination step may further include the aforementioned drying step, etc., as appropriate.

When a further layering step is performed after the layering step, a surface activation treatment step may be performed after the exposure step, after the heating step, or after the metal layer formation step. An example of the surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.

The above layering step is preferably performed 2 to 20 times, and 2 to 9 times is even more preferred.

For example, in the resin layer/metal layer/resin layer/metal layer/resin layer/metal layer configuration, a configuration with at least 2 resin layers and no more than 20 resin layers is preferred, and a configuration with at least 2 resin layers and no more than 9 resin layers is even more preferred.

The composition, shape, and thickness of each of the above layers can be the same or different.

In the present invention, it is particularly preferred to form the cured product (resin layer) of the resin composition of the present invention by further covering the metal layer after providing the metal layer. Specifically, there can be mentioned an embodiment in which (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated, or an embodiment in which (a) a film forming step, (d) a heating step and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated. By alternately performing the step of laminating the resin composition layer (resin layer) of the present invention and the step of forming the metal layer, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment step)

The method for manufacturing the laminate of the present invention preferably includes a surface activation treatment step of performing a surface activation treatment on at least a portion of the metal layer and the resin composition layer.

The surface activation treatment step is typically performed after the metal layer formation step. However, the metal layer formation step may also be performed after the aforementioned development step (preferably, after at least one of the heating step and the post-development exposure step).

The surface activation treatment can be performed on at least a portion of the metal layer alone, at least a portion of the exposed resin composition layer alone, or at least a portion of both. It is preferred to perform the surface activation treatment on at least a portion of the metal layer, and preferably, on a portion or all of the area of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the metal layer, the adhesion between the metal layer and the resin composition layer (film) disposed thereon can be improved.

Furthermore, it is preferred to also perform a surface activation treatment on part or all of the exposed resin composition layer (resin layer). By performing a surface activation treatment on the surface of the resin composition layer, the adhesion between the metal layer and the resin layer disposed on the surface activation treated surface can be improved. In particular, when the resin composition layer is hardened, such as during negative tone development, it is less susceptible to damage from the surface treatment, thus facilitating improved adhesion.

Specifically, the surface activation treatment includes plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , or _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and a thiol group after immersion in an aqueous hydrochloric acid solution to remove the oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500~200,000J/ ^m2 , more preferably 1000~100,000J/ ^m2 , and most preferably 10,000~50,000J/ ^m2 .

(Semiconductor device and its manufacturing method)

The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.

The present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured product or a method for manufacturing a laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213-0218 and Figure 1 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference.

[Example]

The following examples further illustrate the present invention. The materials, amounts, ratios, processing details, and steps described in the following examples may be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are by mass.

<Synthesis of Cyclized Resins or Their Precursors>

[Synthesis Example 1: Synthesis of polybenzoyl hexafluoropropane from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4-oxydiphenylformyl chloride Azole prodrug PBO-1

28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 g of N-methylpyrrolidone. Then, 12.1 g (153 mmol) of pyridine was added, and while the temperature was maintained at -10 to 0°C, a solution obtained by dissolving 20.7 g (70.1 mmol) of 4,4'-oxydiphenylformyl chloride in 75 g of N-methylpyrrolidone was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. Then, polybenzoic acid was added. The azole precursor resin was precipitated in 6 liters of water and the water-polybenzoic acid The azole precursor resin mixture was stirred at 500 rpm for 15 minutes. The azole precursor resin was stirred again in 6 liters of water for 30 minutes and filtered again. The precursor resin was dried at 45 °C for 3 days to obtain polyphenylene sulfide. The polybenzoxazole precursor PBO-1. The weight average molecular weight of the azole prodrug PBO-1 is Mw=21500.

Presumably polyphenylene The structure of the azole prodrug PBO-1 is represented by the following formula (PBO-1).

[Synthesis Example 2: Synthesis of Polyimide Precursor PI-1 from Pyromellitic Dianhydride, 4,4-Diaminodiphenyl Ether, and 2-Hydroxyethyl Methacrylate]

14.06 g (64.5 mmol) of pyromellitic dianhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 10 hours. Furthermore, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl₂ was added over 10 minutes while maintaining the temperature at -10±4°C. The viscosity increased during the addition of _SOCl₂ . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -5-0°C over 20 minutes. After the reaction mixture was allowed to react at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was filtered, stirred again in 4 liters of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried at 45°C under reduced pressure for 3 days to obtain polyimide precursor PI-1. The weight-average molecular weight of polyimide precursor PI-1 was 19,000. The obtained polyimide precursor PI-1 is presumed to contain repeating units represented by the following formula (PI-1).

[Synthesis Example 3: Synthesis of polyimide precursor PI-2 from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]

18.98 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether (water content 88 ppm) were mixed and stirred at 60°C for 10 hours. Furthermore, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted into a polyimide precursor using 4,4'-diaminodiphenyl ether using the same method as in Synthesis Example 2. Polyimide precursor PI-2 was obtained using the same method as in Synthesis Example 2. The weight-average molecular weight of polyimide precursor PI-2 was 20,000. It is estimated that the obtained polyimide precursor PI-2 contains repeating units represented by the following formula (PI-2).

[Synthesis Example 4: Synthesis of polyimide precursor PI-3 from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 10 hours. Then, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted into a polyimide precursor using 4,4'-diaminodiphenyl ether using the same method as in Synthesis Example 2. Polyimide precursor PI-3 was obtained using the same method as in Synthesis Example 2. The weight-average molecular weight of polyimide precursor PI-3 was 18,000. It is estimated that the obtained polyimide precursor PI-3 contains repeating units represented by the following formula (PI-3).

[Chemical formula 76]

[Synthesis Example 5: Synthesis of polyimide precursor PI-4 from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (tolidine) and 2-hydroxyethyl methacrylate]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (obtained by drying at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diethylene glycol dimethyl ether (water content 67 ppm) were mixed and stirred at 60°C for 10 hours. Furthermore, 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl using the same method as in Synthesis Example 2. Polyimide precursor PI-4 was obtained using the same method as in Synthesis Example 2. The weight-average molecular weight of polyimide precursor PI-4 was 19,000. It is estimated that the obtained polyimide precursor PI-4 contains repeating units represented by the following formula (PI-4).

[Synthesis Example 6: Synthesis of Polyimide Precursor PI-5]

23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, along with 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran. The mixture was stirred at room temperature (25°C). While stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the reaction heat subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours.

Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of tetrahydrofuran was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 2 hours, 7.17 g of ethanol was added, followed by stirring for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration, resulting in a reaction solution.

The resulting reaction solution was added to 716.21 g of ethanol, resulting in a precipitate of a crude polymer. The resulting crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum-dried to obtain 80.3 g of powdered resin PI-5. The molecular weight of resin 1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. The structure of resin PI-5 is estimated to be represented by the following formula (PI-5).

[Chemical formula 78]

[Synthesis Example 7: Synthesis of Polyimide PBI-1]

In a flask equipped with a capacitor and a stirrer, while removing moisture, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (Tokyo Chemical Industry Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl (Tokyo Chemical Industry Co., Ltd.) were dissolved in 100.0 g of N-methylpyrrolidone (NMP). Subsequently, 11.9 g (45 mmol) of the diamine (AA-1) described below was added, and the mixture was stirred at 25°C for 3 hours and further at 45°C for 3 hours. Next, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. 50 g of N-methylpyrrolidone (NMP) was then added for dilution.

The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was removed by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The resulting resin was dried at 40°C under reduced pressure for one day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000.

The structure of polyimide PBI-1 is estimated to be represented by the following formula (PBI-1).

<Synthesis Example AA-1: Synthesis of Diamine AA-1>

In a flask equipped with a capacitor and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate and cooled to below 5°C. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate and added dropwise to the flask over 1 hour using a dropping funnel. After the addition was complete, the mixture was stirred at below 10°C for 30 minutes, then heated to 25°C and stirred for 3 hours. The reaction solution was then diluted with 600 mL of ethyl acetate ( _CH₃COOEt ) and transferred to a separatory funnel. The solution was then washed with 300 mL of water, 300 mL of saturated sodium bicarbonate solution, 300 mL of dilute hydrochloric acid, and 300 mL of saturated sodium chloride solution, in that order. Following separation and washing, the solution was dried over 30 g of magnesium sulfate, concentrated using a distiller, and vacuum-dried to yield 61.0 g of the dinitro compound (A-1).

27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed into a flask equipped with a capacitor and a stirrer. 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.

Next, 16.2 g of the dinitro compound (A-1) was added gradually over 1 hour and stirred for 30 minutes. The external temperature was raised to 85°C and stirred for 2 hours. After cooling to below 25°C, the mixture was filtered using CELITE (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate solution, followed by washing with 300 mL of water and 300 mL of saturated sodium chloride solution. After separation and washing, the product was dried with 30 g of magnesium sulfate, concentrated using a distiller, and vacuum-dried to obtain 11.0 g of diamine (AA-1).

<Examples and Comparative Examples>

In each Example, the components listed in the following table were mixed to obtain each resin composition. Furthermore, in each Comparative Example, the components listed in the following table were mixed to obtain each comparative composition.

Specifically, the content of each component listed in the table, excluding the solvent, is the amount (parts by mass) listed in the "parts by mass" column of each column in the table.

The solvent content is set so that the solid content concentration of the composition reaches the value shown in the "Solid content concentration (mass %)" in the table. The ratio of each solvent content to the total mass of the solvent (mass ratio) is set to the ratio listed in the "Ratio in Solvent" column in the table.

The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm.

In the table, a “-” indicates that the composition does not contain the corresponding ingredient.

The details of each ingredient listed in the table are as follows.

[Resin]

．PBO-1, PI-1~PI-5, PBI-1: PBO-1, PI-1~PI-4, PBI-1 obtained by the above synthesis example

[Thermoalkali generator]

．B-1~B-5: Compounds represented by the following formulas (B-1)~(B-5)

[Polymerization initiator (free radical polymerization initiator)]

．C-1: IRGACURE OXE 01 (manufactured by BASF)

．C-2: IRGACURE OXE 02 (manufactured by BASF)

．C-3: IRGACURE 369 (manufactured by BASF)

．C-4: Compound with the following structure

[Polymerizable compounds (free radical crosslinking agents)]

． D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)

．D-2: SR-209 (manufactured by Sartomer Company, Inc., compound with the following structure)

． D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor]

．E-1: 2-Nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

． E-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)

．E-3: p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Specific nitrogen-containing compounds]

F-1~F-21: Compounds with the following structures

[Migration inhibitor]

CF-1~CF-4: Compounds with the following structures

[Chemical formula 84]

-Synthesis Example F-1-

In a three-necked flask, 15 g (0.18 mol) of 3-amino-1,2,4-triazole, 36.06 g (0.36 mol) of triethylamine, and 225 mL of dichloromethane were mixed. While stirring at 0°C, 20.51 g (0.20 mol) of chloromethacrylic acid was added dropwise to the flask using a dropping funnel over 1 hour. After the addition, the reaction was continued at room temperature for 4 hours. After the reaction, the mixture was mixed with 200 mL of water and separated to extract the organic layer. This procedure was repeated three times. After drying with sodium sulfate, the mixture was concentrated using a rotary evaporator. After concentration, 27.5 g of a white powder was obtained by recrystallization.

-Synthesis Example F-2~Synthesis Example F-7-

A white powder was obtained by the same operation as in Synthesis Example F-1, except that the chlorinated methacrylic acid used in Synthesis Example F-1 was replaced with various carboxylic acid chlorides.

-Synthesis Example F-8-

A white powder was obtained by the same operation as in Synthesis Example F-1, except that the chlorinated methacrylic acid used in Synthesis Example F-1 was replaced with p-toluenesulfonyl chloride.

-Synthesis Example F-9-

In a three-necked flask, 9.6 g (0.11 mol) of 3-amino-1,2,4-triazole, 0.3 g of dibutyl dilaurophthalate, and 300 mL of acetone were mixed. Under nitrogen flow and stirring at room temperature, a solution prepared by dissolving 10.21 g (0.12 mol) of isopropyl isocyanate in 150 mL of acetone was added dropwise to the flask over 1 hour using a dropping funnel. After the addition, the reaction was continued at 50°C for 6 hours. After the reaction, the product was concentrated using a rotary evaporator. The resulting solid was washed with hexane and recrystallized to obtain 12.1 g of a white powder.

-Synthesis Example F-10-

A white powder was obtained by following the same procedures as in Synthesis Example F-1, except that 3-amino-1,2,4-triazole was replaced with adenine and methyl methacrylate chloride was replaced with isobutylyl chloride.

-Synthesis Example F-11~Synthesis Example F-20-

F-11 to F-20 were also synthesized by replacing the 3-amino-1,2,4-triazole in Synthesis Example F-1 with various azole skeletons and compounds having an amino group, and replacing chlorinated methacrylic acid with various acid chlorides or various isocyanate compounds.

-Synthesis Example F-21-

A waxy white solid was obtained by following the same procedures as in Synthesis Example 9, except that isopropyl isocyanate used in Synthesis Example F-9 was replaced with mPEG5K-isocyanate (Sigma-Aldrich).

-Synthesis Example CF-3-

9.6 g (0.11 mol) of 3-amino-1,2,4-triazole, 11.78 g (0.15 mol) of isopropyl chloride, 6.0 g of sodium hydroxide, and 300 mL of methanol were mixed in a three-necked flask. The reaction was continued at 85°C for 5 hours. After the reaction was completed, ethyl acetate and water were added for separation. The organic layer was dried over sodium sulfate and concentrated using a rotary evaporator. Purification was performed using a silica gel column using an ethyl acetate/hexane = 3/7 (volume ratio) mobile phase to obtain 2.1 g of a white solid.

[Silane coupling agent (metal adhesion improver)]

．G-1~G-3: Compounds with the following structures. In the following structural formulas, Et represents an ethyl group.

[Chemical formula 86]

[Solvent]

．GBL：γ-butyrolactone

．DMSO: dimethyl sulfoxide

．NMP：N-methyl-2-pyrrolidone

．Ethyl lactate: Ethyl lactate

[Other additives]

．I-1: Compound represented by the following formula (I-1)

．I-2: N-phenyldiethanolamine

<Evaluation>

[Evaluation of preservation stability]

For each resin composition or comparative composition in each Example or Comparative Example, the viscosity was measured using an E-type viscometer (day 0). After the resin composition was allowed to stand in a sealed container at 25°C under light-shielded conditions for 14 days, the viscosity was again measured using an E-type viscometer (day 14). The viscosity fluctuation (%) was calculated using the following formula. The obtained viscosity fluctuations were evaluated according to the following evaluation criteria, and the evaluation results are reported in the "Storage Stability" column in the table. A lower viscosity fluctuation indicates higher storage stability.

Viscosity change rate (%) = |100×{1-(viscosity (14 days)/viscosity (0 days))}|

Viscosity measurements are performed at 25°C. Other specifications are in accordance with JIS Z 8803:2011.

-Evaluation Criteria-

A: Viscosity fluctuation is less than 5%.

B: Viscosity fluctuation rate exceeds 5% and is less than 10%.

C: Viscosity fluctuation rate exceeds 10% and is less than 15%.

D: The viscosity change rate exceeds 15%.

[Evaluation of Metal Adhesion]

The resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied in layers onto a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The copper substrate with the resin composition layer or comparative composition layer formed thereon was dried on a hot plate at 100°C for 5 minutes, thereby forming a uniform resin composition layer or comparative composition layer having a thickness as indicated in the "Film Thickness (μm)" column of the table on the copper substrate. Using a stepper (Nikon NSR 2005 i9C), a photomask with a 100μm square non-masked area was used to expose the resin composition layer or the comparative composition layer on a copper substrate with i-rays at an exposure energy of 500mJ/ ^cm² . The layer was then developed for 60 seconds using the developer listed in the "Developer" column of the table and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100μm square resin layer. Furthermore, the resin layer (pattern) was formed by heating the layer in a heating oven at the temperature listed in the "Curing Temperature (°C)" column of the table for the time listed in the "Curing Time (min)" column of the table in a nitrogen atmosphere.

The shear force of a 100μm square resin layer on a copper substrate was measured using an adhesive strength tester (manufactured by XYZTEC, CondorSigma) at 25°C and 65% relative humidity (RH). It is believed that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. In all examples and comparative examples, the shear force exceeded 30gf.

[Evaluation of post-HTS (High Temperature Strage-test) bonding strength]

The resin layer and copper substrate were heated at the temperature listed in the "Curing Temperature (°C)" column of the table for the time listed in the "Curing Time (min)" column of the table. Afterwards, the layers were placed in a constant temperature bath at 175°C for 1000 hours. Shear force was measured using the same evaluation method as described above for metal adhesion, and post-heating metal adhesion was evaluated. Based on the measured shear force, the following evaluation criteria were used to evaluate the results, which are reported in the "Post-HTS Adhesion Strength" column of the table. The greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. Furthermore, the better the post-HTS adhesion, the less likely it is to delaminate between the cured film and the metal, even over extended periods of time.

-Evaluation Criteria-

A: The shear force exceeded 30gf.

B: Shear force exceeds 25gf and is less than 30gf.

C: Shear force is less than 25gf.

Also, 1gf is 0.00980665N.

[Evaluation of void volume after HTS]

Using the same method as the aforementioned evaluation of metal adhesion, a 100μm square resin layer was formed on a copper substrate.

The resin layer and copper substrate were heated at the temperature listed in the "Curing Temperature (°C)" column of the table for the time listed in the "Curing Time (min)" column of the table. After 1000 hours in a constant temperature chamber at 175°C, cross-sectional SEM (scanning microscope) measurements were performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula.

Void area ratio (%) = (area of voids observed by SEM) / (total area of resin layer) × 100

Based on the obtained void area ratio values, the following evaluation criteria were used for evaluation. The evaluation results are reported in the "Void Amount after HTS" column of the table. The smaller the void area ratio, the better the reliability of the hard coating after HTS. It can be said that even after a long period of time, voids are less likely to form between the metal layer and the hardened product.

A: The void area ratio is less than 0.5%.

B: The void area ratio exceeds 0.5% and is 2% or less.

C: The void area ratio is 2% or more.

<Example 101>

In the evaluation of metal adhesion, post-HTS adhesion, and post-HTS void content, an infrared lamp heater (RTP-6, manufactured by ADVANCE RIKO, Inc.) was used as the heating mechanism for heating the resin layer and copper substrate at the temperature listed in the "Curing Temperature (°C)" column for the time listed in the "Curing Time (min)" column. The storage stability, post-HTS adhesion, and post-HTS void content were evaluated under the same conditions as in Example 1, using the same resin composition.

In the evaluation of storage stability, the evaluation of adhesion after HTS, and the evaluation of void volume after HTS, the same results as those of Example 1 were obtained.

<Example 102>

In the resin composition used in Example 1, the thermal alkali generator was changed from B-1 to the same mass fraction of the following B-6, and the heating temperature of the resin layer and copper substrate was set at 200°C. Evaluations of storage stability, post-HTS adhesion, and post-HTS void content were conducted under the same conditions as in Example 1.

In the evaluation of storage stability, the evaluation of adhesion after HTS, and the evaluation of void volume after HTS, the same results as those of Example 1 were obtained.

<Example 103>

In Example 8, the resin was replaced with the same mass of resin PI-5 and the photoalkali generator B-1 was replaced with the same mass of photoalkali generator B-7, thereby preparing a curable resin composition for forming a positive-type curable resin film. The resulting curable resin composition was used to evaluate storage stability, adhesion after HTS, and void content after HTS.

The evaluation of storage stability was carried out using the same method as in Example 8.

Evaluations of adhesion and post-HTS void content were conducted using the same method as in Example 8, except that the photomask was changed to one with a 100 μm square mask portion, and the pattern was formed by developing with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds and rinsing with pure water.

The same evaluations as in Example 8 were performed, and the results of the evaluations of storage stability, adhesion after HTS, and void volume after HTS were similar, even for the positive type.

The evaluation results for storage stability, post-HTS adhesion, and post-HTS void volume were the same as those in Example 8.

<Example 104>

In Example 1, a resin composition was prepared by the same method as in Example 1, except that the amount of resin PI-3 was changed from 80 parts by mass to 86.7 parts by mass, in addition to the alkali generator B-1, polymerization initiator C-1, polymerization inhibitor E-2, and silane coupling agent G-1.

Using the above resin composition, the storage stability, post-HTS adhesion, and post-HTS void content were evaluated using the same methods as in Example 1. The results obtained for each evaluation item were the same as those in Example 1.

<Example 105>

In Example 8, the following description was changed from "exposure was performed using a photomask with a 100 μm square non-mask portion formed thereon, using i-rays" to "exposure was performed using a direct exposure apparatus (ADTEC DE-6UH III) on a 100 μm square area." Evaluation was performed using the same method as in Example 8. The same results as in Example 8 were obtained for all evaluation items.

The above results indicate that the cured product formed from the resin composition of the present invention exhibits excellent adhesion after HTS.

The comparative compositions in Comparative Examples 1 to 4 do not contain the specific nitrogen-containing compound. In these cases, the resulting cured products exhibit poor adhesion after HTS.

<Example 201>

The resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate with a copper thin layer formed on the surface by spin coating. After drying at 100°C for 5 minutes, a 20μm-thick photosensitive film was formed. Exposure was then performed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a 1:1 line-space pattern and a line width of 10μm). After heating, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.

Next, the temperature was raised in a nitrogen atmosphere at a rate of 10°C/minute to 180°C, where it was maintained for 120 minutes, forming an interlayer insulating film for the redistribution layer. This interlayer insulating film exhibited excellent insulating properties.

Furthermore, semiconductor devices were fabricated using these interlayer insulating films for redistribution layers, and normal operation was confirmed.

without.

Claims (13)

A resin composition comprising a cyclized resin or a precursor thereof and a nitrogen-containing compound, wherein the nitrogen-containing compound contains a nitrogen-containing heterocyclic ring and an amino group in the same compound, one of the hydrogen atoms of the amino group may be substituted, and at least one of the nitrogen atoms serving as a ring member of the nitrogen-containing heterocyclic ring is directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group, and the molecular weight of the nitrogen-containing compound is less than 2000. The resin composition as described in claim 1, wherein the nitrogen-containing heterocyclic ring comprises an imidazole skeleton, a triazole skeleton, or a tetrazole skeleton. The resin composition as described in claim 1 or claim 2, wherein the aforementioned amino group contained in the aforementioned nitrogen-containing compound is unsubstituted. The resin composition according to claim 1 or claim 2, wherein the chain length of the linking chain between the nitrogen atom as a ring member of the nitrogen-containing heterocyclic ring contained in the nitrogen-containing compound and the nitrogen atom of the amino group is 3 or less. The resin composition as described in claim 1 or claim 2, wherein the nitrogen atom serving as a ring member of the aforementioned nitrogen-containing heterocyclic ring contained in the aforementioned nitrogen-containing compound is directly bonded to the carbonyl group. The resin composition according to claim 1 or claim 2, wherein the nitrogen-containing compound is a compound represented by any one of the following formulas (1-1), (2-1), or (3-1); In formula (1-1), ^R1 represents a monovalent organic group, ^R1a each independently represents a hydrogen atom or a substituent, and ^RN1 represents a hydrogen atom or a substituent; in formula (2-1), ^R2 represents a monovalent organic group, ^R2a represents a hydrogen atom or a substituent, and ^RN2 represents a hydrogen atom or a substituent; in formula (3-1), ^R3 represents a monovalent organic group, and ^RN3 represents a hydrogen atom or a substituent. The resin composition as described in claim 1 or claim 2 is used to form an interlayer insulating film for a redistribution layer. A cured product obtained by curing the resin composition described in any one of claims 1 to 7. A laminate comprising two or more layers formed of the hardened material as claimed in claim 8, and comprising a metal layer between any of the layers formed of the hardened material. A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any one of claims 1 to 7 to a substrate to form a film. The method for producing a cured product as described in claim 10 includes an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern. The method for producing a cured product as described in claim 10 includes a heating step of heating the film at 50-450°C. A semiconductor device comprising the hardened material according to claim 8.