TWI886114B - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device and thermal alkali generator - Google Patents

Abstract

The present invention provides a curable resin composition containing a heterocyclic polymer precursor and a compound represented by the following formula (1-1), a cured film formed by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a semiconductor device containing the cured film or the laminate. In addition, a novel thermal alkali generator is provided. In formula (1-1), R1 and R2 each independently represent a monovalent organic group, L1 represents a divalent linking group, R3 represents a hydrogen atom or a monovalent organic group, and R1 and R2 can be bonded to form a ring structure.

Description

Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device and thermal alkali generator

The present invention relates to a curable resin composition containing a heterocyclic polymer precursor, a cured film, a laminate, a method for producing the cured film, a semiconductor device and a thermal alkali generator.

The resin obtained by cyclizing and curing a precursor of a heterocyclic polymer such as a polyimide resin or a polybenzoxazole resin (also referred to as a "heterocyclic polymer precursor") has excellent heat resistance and insulation properties and is therefore suitable for various uses. The above uses are not particularly limited, but if the actual semiconductor device for mounting is taken as an example, the use as a material or protective film for an insulating film or sealing material can be cited. In addition, it is also used as a base film or cover layer of a flexible substrate.

For example, in the above-mentioned application, the hybrid ring-containing polymer precursor is used as a curable resin composition containing the hybrid ring-containing polymer precursor. The curable resin composition is applied to a substrate by coating, etc., and then the hybrid ring-containing polymer precursor is cyclized by heating, etc., so that a cured resin can be formed on the substrate. The curable resin composition can be applied by a known coating method, etc., so it can be said that the curable resin composition has excellent manufacturing adaptability, such as high degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition. In addition to the high performance of polyimide resins, they also have excellent manufacturing adaptability. There is an increasing expectation for the expansion of industrial applications of curable resin compositions containing heterocyclic polymer precursors.

For example, Patent Document 1 describes a thermosetting resin composition comprising a thermal alkali generator and a thermosetting resin, wherein the thermal alkali generator comprises at least one selected from an acidic compound that generates a base when heated to 40° C. or higher and an ammonium salt having an anion and an ammonium cation with a pKa1 of 0 to 4.

Furthermore, Patent Document 2 describes a curable resin composition containing a polyimide precursor having specific structural units and a compound that generates free radicals when irradiated with actinic rays.

[Patent Document 1] International Publication No. 2015/199219 [Patent Document 2] Japanese Patent Publication No. 2014-201695

In a curable resin composition containing a heterocyclic polymer precursor such as a polyimide precursor, it is expected to provide a curable resin composition that is not easily cyclized during storage (for example, storage at room temperature (25°C, hereinafter the same)), and the obtained cured product has excellent elongation at break. In this specification, the fact that the curable resin composition is not easily cyclized during storage is also referred to as "the curable resin composition has excellent storage stability".

One aspect of the present invention aims to provide a curable resin composition having excellent storage stability and a cured film having excellent elongation at break, a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for manufacturing the cured film, and a semiconductor device comprising the cured film or the laminate. In addition, another aspect of the present invention aims to provide a novel thermal alkali generator.

<1> A curable resin composition comprising a heterocyclic polymer precursor and a compound represented by the following formula (1-1): [Chemical Formula 1] In formula (1-1), ^R1 and ^R2 are independently a monovalent organic group, ^L1 is a divalent linking group, ^R3 is a hydrogen atom or a monovalent organic group, and ^R1 and ^R2 may be bonded to form a ring structure. <2> The curable resin composition as described in <1>, wherein the above ^L1 is a divalent linking group with a linking chain length of 1 to 5. <3> The curable resin composition as described in <1> or <2>, wherein the above ^R1 and ^R2 are independently a alkyl group. <4> The curable resin composition according to any one of <1> to <3>, wherein ^L1 is 1,2-ethylene, 1,3-propanediyl, 1,2-cyclohexanediyl, cis-vinylene, 1,2-phenylene, 1,2-phenylenemethylene or 1,2-ethoxy-1,2-ethylene. <5> The curable resin composition according to any one of <1> to <4>, wherein ^R3 is a hydrogen atom, an alkyl group or an aryl group. <6> The curable resin composition according to any one of <1> to <5>, wherein the molecular weight of the compound represented by the above formula (1-1) is 100 or more and 2,000 or less. <7> The curable resin composition according to any one of <1> to <6>, further comprising a photoradical polymerization initiator and a radical polymerizable compound. <8> The curable resin composition as described in any one of <1> to <7>, which comprises at least one prodriver selected from the group consisting of polyimide prodrivers and polybenzoxazole prodrivers as the heterocyclic polymer prodriver. <9> The curable resin composition as described in any one of <1> to <8>, which comprises a polyimide prodriver as the heterocyclic polymer prodriver. <10> The curable resin composition as described in <9>, wherein the polyimide prodriver has a repeating unit represented by the following formula (1), [Chemical Formula 2] In formula (1), ^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. <11> The curable resin composition as described in <10>, wherein at least one of ^R113 and ^R114 in the above formula (1) contains a radical polymerizable group. <12> The curable resin composition as described in any one of <1> to <11>, which is used for forming an interlayer insulating film for a redistribution layer. <13> A cured film formed by curing the curable resin composition as described in any one of <1> to <12>. ＜14＞ A laminate comprising two or more layers of the cured film described in ＜13＞, wherein a metal layer is included between any of the cured films. ＜15＞ A method for producing a cured film, comprising a film forming process of applying the curable resin composition described in any one of ＜1＞ to ＜12＞ to a substrate to form a film. ＜16＞ The method for producing a cured film as described in ＜15＞, further comprising a heating process of heating the film to decompose the compound represented by the above formula (1-1). ＜17＞ A semiconductor device comprising the cured film described in ＜13＞ or the laminate described in ＜14＞. ＜18＞ A thermal alkali generator represented by the following formula (1-2), wherein [Chemical Formula 3] In formula (1), R ²¹ and R ²² each independently represent a monovalent organic group, L ²¹ represents a divalent linking group, the atoms in the bonding positions at both ends of L ²¹ are carbon atoms, and R ²³ represents a hydrogen atom or a monovalent organic group. [Effects of the Invention]

According to one aspect of the present invention, a curable resin composition having excellent storage stability and excellent elongation at break of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate can be provided. In addition, according to another aspect of the present invention, a new type of thermal alkali generator is provided.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range indicated by the symbol "～" indicates a range including the numerical values before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only indicates an independent process, but also includes processes that cannot be clearly distinguished from other processes as long as the desired effect of the process can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes exposure using particle beams such as electron beams and ion beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, there can be cited actinic radiation or radiation such as the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "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 means the total mass of the components excluding the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement) and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV (ultraviolet) wavelength 254nm detector. In this specification, when the position of each layer constituting a laminate is recorded as "up" or "down", it is sufficient that other layers exist on the upper side or the lower side of the layer serving as a reference among the plurality of layers concerned. That is, a third layer or a third element may be further sandwiched between the layer serving as a reference and the other layers mentioned above, and the layer serving as a reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction of stacking layers relative to the substrate is referred to as "up", or when a photosensitive layer exists, the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of these up and down directions is for the convenience of this specification, and in actual forms, the "up" direction in this specification may also be different from the vertically upward direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds that meet the requirements of the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds that meet the requirements of the component. In this specification, unless otherwise specified, the physical property values are values under the conditions of a temperature of 23°C and an air pressure of 101325Pa (1 atmosphere). In this specification, a combination of the best form is a more preferred form.

(Curing resin composition) The curable resin composition of the present invention (hereinafter referred to as "the composition of the present invention") contains a heterocyclic polymer precursor and a compound represented by formula (1-1). In addition, the curable resin composition of the present invention preferably also contains a photoradical polymerization initiator and a radical polymerizable compound described below.

The curable resin composition of the present invention has excellent storage stability and the obtained cured film has excellent elongation at break. The mechanism for obtaining the above effect is not clear, but it can be inferred as follows. It is believed that the compound represented by formula (1-1) contained in the curable resin composition of the present invention is not easily decomposed when stored at room temperature, so it has excellent storage stability. In addition, when curing is performed by heating, the base generation efficiency is excellent, so the cyclization of the heterocyclic polymer precursor is easy to proceed, and the obtained cured film has excellent elongation at break. Furthermore, it is believed that since the curable resin composition contains the compound represented by formula (1-1), the cyclization of the heterocyclic polymer precursor is easily carried out by heating or the like as described above, and thus the adhesion to a substrate such as copper is also easily excellent. In other words, it is believed that by using the curable resin composition of the present invention, a laminate having excellent interlayer adhesion is easily obtained.

However, in Patent Documents 1 and 2, there is neither description nor suggestion regarding a curable resin composition containing a compound represented by Formula (1-1). The components contained in the curable resin composition of the present invention are described in detail below.

<Hybrid ring-containing polymer precursor> The curable resin composition of the present invention contains a heterocyclic polymer precursor. As the above-mentioned heterocyclic polymer precursor, the curable resin composition of the present invention preferably contains at least one precursor selected from the group including polyimide precursors and polybenzoxazole precursors, and more preferably contains polyimide precursors.

[Polyimide Precursor] From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the following formula (1). [Chemical Formula 4]

In formula (1), ^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.

^-A1 and ^A2- In the formula (1), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, and an oxygen atom is preferably an oxygen atom.

-R ¹¹¹ - R ¹¹¹ in formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group combining two or more of these groups. 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 comprising a combination thereof is preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred.

R ¹¹¹ in formula (1) 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. The diamine may be used alone or in combination of two or more.

Specifically, the diamine is preferably a diamine including a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group including these combinations, and more preferably a diamine including an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[Chemical formula 5]

In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) _2- , -NHC(=O)-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, and -S(=O) _2- ; and even more preferably a divalent group selected from the group consisting of _-CH2- , -O-, -S-, -S(=O) _2- , -C( _CF3 ) _2- , and -C( _CH3 ) _2- .

As the diamine, specifically, there can be mentioned 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 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'-dimethylcyclohexyl Methane or isophorone diamine; meta-phenylenediamine or para-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone or 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminodiphenyl Aminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 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)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminotriphenylene glycol Benzene, 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'-diaminodiphenylmethane Aminodiphenylmethane, 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-(3',5'-diaminobenzyloxy)ethyl methacrylate, 2,4-diaminocumene or 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, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoro Propane, 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- At least one diamine selected from the group consisting of 2,4'-bis(trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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'-hexafluorotoluidine and 4,4'-diaminoquaternaryl.

Furthermore, the diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical formula 6]

[Chemical formula 7]

As a preferred example, a diamine having at least two alkylene glycol units in the main chain can also be cited. Preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, or both, and more preferably, it is a diamine that does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) The present invention includes, but is not limited to, EDR-176, D-200, D-400, D-2000, D-4000 (the above trade names are manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.

The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176 are shown below.

[Chemical formula 8]

In the above, x, y, and z are arithmetic means.

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ in formula (1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ⁰ -. Ar ⁰ is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. ^{L 0} represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO-, and a combination of two or more of these groups. The preferred range of L ⁰ has the same meaning as that of A above.

From the viewpoint of i-ray transmittance, R ¹¹¹ in formula (1) 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.

[Chemical formula 9]

In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the monovalent organic group for 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 10]

In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound that gives the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these compounds may be used alone, or two or more thereof may be used in combination.

-R ¹¹⁵ - R ¹¹⁵ in formula (1) 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 (6).

[Chemical formula 11]

R ¹¹² has the same meaning as A, and the preferred range is also the same.

As the tetravalent organic group represented by R ¹¹⁵ in formula (1), specifically, there can be mentioned the tetracarboxylic acid residue remaining after removing the acid dianhydride group from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. It is preferred that the tetracarboxylic dianhydride is a compound represented by the following formula (7).

[Chemical formula 12]

R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1).

Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic 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 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic 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 - at least one of 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 their alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below can be cited.

[Chemical formula 13]

-R ¹¹³ and R ¹¹⁴ - R ¹¹³ and R ¹¹⁴ in formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of ^{R 113} and R ¹¹⁴ is a repeating unit containing a free radical polymerizable group, and it is more preferred that both contain a free radical polymerizable group. The free radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a free radical, and a group having an ethylenic unsaturated bond can be cited as a preferred example.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryl group, and a group represented by the following formula (III).

[Chemical formula 14]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred.

In formula (III), ^R201 represents an alkylene group having 2 to 12 carbon atoms, _-CH2CH (OH) _CH2- , or a (poly)oxyalkylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly)oxyalkylene group represents an oxyalkylene group or a polyoxyalkylene group. Preferred examples of ^R201 include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and _-CH2CH (OH) _CH2- . More preferred examples include ethylene, propylene, trimethylene, and _-CH2CH (OH) _CH2- . It is particularly preferred that R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylidene group. As a preferred embodiment of the polyimide precursor in the present invention, the monovalent organic group of R ¹¹³ or R ¹¹⁴ includes 1, 2 or 3 acid groups, preferably an aliphatic group, an aromatic group and an aralkyl group having one acid group. Specifically, an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms can be mentioned. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ is preferably a group having a hydroxyl group. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility in a developer solution can be preferably used.

From the viewpoint of solubility in aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, ^R113 or ^R114 is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferred, and an alkyl group substituted with an aromatic group is more preferred.

The number of carbon atoms in the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. Examples of the straight chain or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic alkyl group include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, borndiyl, bicyclohexyl and pinenyl. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group as described below is preferred.

The aromatic group may be specifically a substituted or unsubstituted aromatic alkyl group (as the ring structure constituting the group, there may be mentioned a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenyl ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a chrysene ring, a tris-extended benzene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (as the ring structure constituting the group, there may be mentioned a fluorene ring, a biphenyl ring, a pyridine ring, a cyclopentane ... (a) a pyrrolyl ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a pyrimidine ring, an indole ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolyl ring, a quinoline ring, a pyrrolyl ring, a naphthridine ring, a quinoline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthracene ring, a chromene ring, a pyrrolidine ring, a phenanthryl ring, a phenanthryl ring, a phenanthryl ring or a phenanthryl ring).

In addition, it is also preferred that the polyimide precursor has fluorine atoms in the repeating unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is practically 50% by mass or less.

In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The repeating unit represented by formula (1) is preferably a repeating unit represented by formula (1-A) or (1-B).

[Chemical formula 15]

^A11 and ^A12 represent an oxygen atom or -NH-, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of ^R113 and ^R114 is preferably a group containing a free radical polymerizable group, and more preferably a free radical polymerizable group.

The preferred ranges of A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as the preferred ranges of A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively.

The preferred range of R ¹¹² is the same as that of R ¹¹² in formula (5), wherein oxygen atom is more preferred.

The bonding position of the carbonyl group to the benzene ring is preferably 4, 5, 3', or 4' in formula (1-A). In formula (1-B), 1, 2, 4, or 5 is preferred.

In the polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. Furthermore, the repeating unit represented by formula (1) may contain structural isomers. Furthermore, in addition to the repeating unit of the above formula (1), the polyimide precursor may also contain other types of repeating units.

As an embodiment of the polyimide precursor of the present invention, 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total repeating units are repeating units represented by formula (1). The upper limit is practically 100 mol% or less.

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

The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3. In this specification, the molecular weight dispersion is the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

The polyimide precursor can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, the precursor is obtained by halogenating the dicarboxylic acid or the dicarboxylic acid derivative with a halogenating agent and then reacting the diamine with the dicarboxylic acid.

In the method for producing a polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds.

The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone, and N-ethylpyrrolidone.

When manufacturing the polyimide precursor, a process including solid precipitation is preferred. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, thereby enabling solid precipitation.

[Polybenzoxazole precursor] The polybenzoxazole precursor preferably comprises a repeating unit represented by the following formula (2). [Chemical formula 16]

In formula (2), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

-R ¹²¹ - In formula (2), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms) is preferred. As an aromatic group constituting R ¹²¹ , R ¹¹¹ of the above formula (1) can be cited as an example. As the above aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably derived from 4,4'-oxydiphenylformyl chloride.

-R ¹²² - In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (1) above, and the preferred range is also the same. R ¹²² is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

-R ¹²³ and R ¹²⁴ - R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and have the same meanings as R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferred ranges are also the same.

In addition to the repeating units of the above formula (2), the polybenzoxazole precursor may also contain other types of repeating units.

From the viewpoint of being able to suppress the occurrence of warping of the cured film accompanying ring closure, the polybenzoxazole precursor preferably further contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[Chemical formula 17]

Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R ^2s is a alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), and they may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. In the Z part, it is preferred that the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a+b is 100 mol%.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by a commonly used gel permeation chromatography method. By setting the molecular weight to the above range, the effect of reducing the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor and suppressing warping and the effect of improving solubility can be achieved.

When the polybenzoxazole precursor contains a diamine residue represented by the formula (SL) as another type of repeating unit, it is preferred to further contain a tetracarboxylic acid residue remaining after removing the dianhydride group from tetracarboxylic dianhydride as a repeating unit from the viewpoint of improving the alkali solubility of the curable resin composition. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in the formula (1).

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

The molecular weight dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the heterocyclic polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and still further preferably 70% by mass or more, relative to the total solid content of the composition. In addition, the content of the heterocyclic polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and still further preferably 95% by mass or less, relative to the total solid content of the composition.

The curable resin composition of the present invention may contain only one heterocyclic polymer precursor or two or more. When two or more heterocyclic polymer precursors are contained, the total amount is preferably within the above range.

<Compound represented by formula (1-1)> The curable resin composition of the present invention contains a compound represented by formula (1-1). [Chemical formula 18]

In formula (1-1), ^R1 and ^R2 each independently represent a monovalent organic group, ^L1 represents a divalent linking group, ^R3 represents a hydrogen atom or a monovalent organic group, and ^R1 and ^R2 may be bonded to form a ring structure.

The compound represented by formula (1-1) is preferably a compound that decomposes to generate a base. Furthermore, when the curable resin composition is cured by heat, the compound represented by formula (1-1) is more preferably a compound that decomposes by heat to generate a base. That is, the compound represented by formula (1-1) is preferably a base generator, and a thermal base generator is more preferably. For example, it is believed that the compound represented by the following formula (B-1) is decomposed by heating, for example, as described in the following reaction formula, and the generated diisopropylamine acts as a base, thereby promoting the cyclization of the heterocyclic polymer precursor in the curable resin composition. [Chemical Formula 19]

^-R1 and ^R2- In formula (1-1), ^R1 and ^R2 are each independently preferably a alkyl group, more preferably a alkyl group having 1 to 20 carbon atoms, and more preferably a alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, and even more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or phenyl is preferred, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl is further preferred, and methyl, ethyl, isopropyl or cyclohexyl is the most preferred. Furthermore, ^R1 and ^R2 may be bonded to form a ring structure, and the formed ring structure is preferably an aliphatic ring structure having 5 or 6 ring members, and more preferably a pyrrolidine ring, a piperidine ring, a piperidine ring, or a morpholine ring structure. The formula weight (the sum of the atomic weights of the atoms contained in ^R1 or ^R2 ) of ^R1 and ^R2 is preferably 29 to 300, more preferably 57 to 282, and even more preferably 57 to 200, respectively. In addition, regarding ^R1 and ^R2 of the generated base, from the viewpoint that the basicity of the generated base becomes high and the interaction between the generated base and the substrate such as the copper substrate is small, and the adhesion between the obtained cured film and the substrate is improved, ^R1 and ^R2 are each independently an alkyl group having 1 to 10 carbon atoms, or ^R1 and ^R2 are bonded to form an aliphatic ring structure having 5 or 6 ring members. It is more preferred that ^R1 and ^R2 are each independently an ethyl group or an isopropyl group, or ^R1 and ^R2 are bonded to form a piperidine ring structure. In addition, the structures of R1 and ^R2 can be selected by considering, for example, the strength of the alkalinity of the generated base, the strength of the interaction between the generated base and the substrate, the mobility of the generated base, the interaction between the generated base and ^other materials in the film, etc.

-L ¹ - In formula (1-1), L ¹ is preferably a divalent linking group with a linking chain length of 1 to 5, and more preferably a divalent linking group with a linking chain length of 2 or 3. In the present specification, the linking chain length of L ¹ represents the smallest number of atoms contained in L ¹ and between two carbon atoms C ¹ and C ² in the compound represented by the following formula (1-1'). The following formula (1-1') is obtained by writing C ¹ and C ² labels for carbon atoms in the above formula (1-1), and R ¹ , R ² , R ³ and L ¹ in formula (1-1') have the same meanings as R ¹ , R ² , R ³ and L ¹ in formula (1-1), respectively. For example, in the compound represented by the above formula (B-1), ^L1 is 1,2-phenylene and the length of the linking chain is 2. [Chemical Formula 20]

It is preferred that the atoms at the bonding positions at both ends of L ¹ are carbon atoms. The bonding positions at both ends of L ¹ represent two places, namely, the bonding site between L ¹ and carbon atom C ¹ and the bonding site between L ¹ and carbon atom C ² in the above formula (1-1'). From the viewpoint of the efficiency of base generation, it is preferred that the structure between carbon atom C ¹ and carbon atom C ² in L ¹ is a part of an aromatic ring structure or an unsaturated aliphatic hydrocarbon structure, and a phenylene group (particularly preferably 1,2-phenylene group) or a cis-ethylene group is more preferred. The phenylene group or cis-ethylene group may further have a known substituent. In addition, L ¹ may further have a base generating site in a structure other than the structure between carbon atom C ¹ and carbon atom C ² . As the base generating site, for example, a structure other than ^L1 in the above formula (1-1) (a combination of two structures described in the following formula (1-1A)) can be cited. As an example of a compound in which ^L1 further includes a base generating site in a structure other than the structure existing between carbon atom ^C1 and carbon atom ^C2 , compounds represented by the following formulas (B-16, B-17, B-18) can be cited. In addition, for example, the structure of ^L1 can be selected in consideration of the base generating efficiency. [Chemical Formula 21] In formula (1-1A), * independently represents a bonding site with other structures, and R ^1A , R ^2A and R ^3A have the same meanings as R ¹ , R ² and R ³ in formula (1-1), respectively, and preferred embodiments are also the same. In the two structures in formula (1-1A), the linking chain length is preferably bonded through 1 to 5 linking groups, and the linking chain length is preferably bonded through 2 or 3 linking groups. In addition, the structure between the two structures in formula (1-1A) is preferably a part of an aromatic ring structure or an unsaturated aliphatic hydrocarbon structure.

^L1 is also preferably a alkyl group. As the alkyl group, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, or an arylene group is preferred, an alkylene group having 2 to 3 carbon atoms, an alkenylene group having 2 to 3 carbon atoms, or a phenylene group is more preferred, an alkenylene group having 2 to 3 carbon atoms, or a phenylene group is more preferred, and a vinylene group or a phenylene group is more preferred.

Moreover, ^L1 is preferably 1,2-ethylene, 1,3-propanediyl (trimethylene), 1,2-cyclohexanediyl, cis-vinylene, 1,2-phenylene, 1,2-phenylenemethylene or 1,2-ethoxy-1,2-ethylene, and more preferably cis-vinylene or 1,2-phenylene.

-R ³ - R ³ is preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aryl group, more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and still more preferably an alkyl group having 2 to 8 carbon atoms or a phenyl group. From the viewpoint that the interaction between the generated base and the substrate such as a copper substrate is small and the adhesion between the obtained cured film and the substrate is improved, an alkyl group having 2 to 4 carbon atoms or a phenyl group is more preferred. When R ³ is an alkyl group, the alkyl group may be any structure of a linear chain or a branched chain, and may be a structure having a ring structure. From the viewpoint of the efficiency of base generation, a linear chain structure is preferred. In addition, for example, the structure of R ³ can be selected in consideration of the efficiency of alkali generation, the strength of the interaction between the decomposed compound and a substrate such as a copper substrate, the strength of the electron donating property, and the like.

-Molecular weight- The molecular weight of the compound represented by formula (1-1) can be determined by considering, for example, the decomposition temperature, volatility, etc., and is preferably 100 or more, more preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more. There is no particular upper limit, but 1,000 or less is preferred.

-Decomposition temperature- When the compound represented by formula (1-1) is a thermal alkali generator, the decomposition temperature is preferably 50°C or higher, more preferably 80°C or higher, more preferably 120°C or higher, and more preferably 140°C or higher. As the upper limit, 450°C or lower is more preferably, 350°C or lower is more preferably, and 250°C or lower is more preferably. By setting the decomposition temperature to a lower temperature, the energy required for curing of the curable resin composition can be reduced. On the other hand, by setting the decomposition temperature to a value higher than the lower limit, the inadvertent generation of alkali during storage at room temperature or the like is suppressed to promote curing, thereby improving the storage stability of the curable resin composition. When the compound represented by formula (1-1) is heated to 500°C in a pressure-resistant capsule at 5°C/min, the peak temperature of the lowest exothermic peak is determined as the decomposition temperature.

As specific examples of the compound represented by formula (1-1), the following compounds can be cited, but the present invention is not limited to these compounds. [Chemical Formula 22] [Chemical formula 23]

These compounds can be synthesized, for example, by reacting an acid anhydride compound with an amine compound to synthesize an acylamide compound, and then by a condensation reaction of the acylamide compound with an amine compound. The acid anhydride compound and the amine compound can be appropriately selected in consideration of the structure of the final compound to be obtained. Specifically, the synthesis can be performed using the method described in Organic Chemistry International (2014), 576715/1-576715/10, page 10, etc.

In the compound represented by formula (1-1), the pKa of the co-acting acid of the generated base is preferably 8 or more, more preferably 9 or more, and further preferably 10 or more. There is no particular upper limit, and it is actually 14 or less. By setting the pKa of the specific thermal alkali generator to the above range, the generated base can efficiently carry out the cyclization reaction of the heterocyclic polymer precursor and can improve the elongation at break of the cured film at low temperature, which is better from this point of view. The pKa here is set to a value determined by the following method. The pKa described in this specification is a dissociation reaction of releasing hydrogen ions from oxygen and the equilibrium constant Ka is expressed by the negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is calculated based on ACD/ChemSketch (registered trademark). Alternatively, you may refer to the values listed in "Chemical Handbook: Basics, 5th Edition" edited by the Chemical Society of Japan.

From the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film, the content of the compound represented by formula (1-1) is preferably 0.005 to 50 mass % relative to the total solid content concentration of the curable resin composition. The lower limit is more preferably 0.05 mass % or more, more preferably 0.5 mass % or more, and particularly preferably 1 mass % or more. From the viewpoint of corrosion resistance of metals (e.g., copper used for wiring, etc.), the upper limit is more preferably 20 mass % or less, more preferably 10 mass % or less, and particularly preferably 5 mass % or less.

From the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film, the content of the compound represented by formula (1-1) is preferably 0.005 parts by mass or more, more preferably 0.06 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of the heterocyclic polymer precursor. From the viewpoint of corrosion resistance of metals (e.g., copper used for wiring, etc.), the upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 7.5 parts by mass or less. The compound represented by formula (1-1) can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Other alkali generators> The curable resin composition of the present invention may contain other alkali generators. Other alkali generators do not include the compound represented by the above formula (1-1). As other alkali generators, thermal alkali generators and photoalkali generators can be cited. When other thermal alkali generators are included, those described in International Publication No. 2015/199219 and International Publication No. 2015/199220 are exemplified, and the contents are incorporated into this specification. In addition, in the present invention, it is also possible to set a structure that substantially does not contain other thermal alkali generators. “Substantially free of” means that in the curable resin composition of the present invention, the content of other alkali generators is 5 mass % or less, preferably 3 mass % or less, and more preferably 1 mass % of the content of the compound represented by formula (1-1).

<Photopolymerization initiator> The curable resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, an activator that reacts with a photoexcited sensitizer to generate active radicals can be used.

The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol ^-1 ·cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can also be preferably used. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength that matches a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can also be used.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

As the photo-radical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Among oxime compounds, the exposure tolerance (exposure margin) is wide and they also function as photohardening accelerators, so they are particularly preferred.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the curable resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 24]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471.

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to select at least one compound from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is further preferred to use metallocene compounds or oxime compounds, and it is further preferred to use oxime compounds.

In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-aminophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-amino-propanone-1, quinones obtained by condensation of an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, compounds represented by the following formula (I) may be used.

[Chemical formula 25]

In the 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, a phenyl group, a phenyl group substituted by 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 interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R ¹⁰¹ is a group represented by the formula (II) or is 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.

[Chemical formula 26]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Furthermore, the photoradical polymerization initiator may include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The photopolymerization initiator may be contained in one type or in two or more types. When two or more photopolymerization initiators are contained, the total amount thereof is preferably within the above range.

<Thermal polymerization initiator> As a polymerization initiator, the curable resin composition of the present invention may include a thermal polymerization initiator, and in particular, may include a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the heterocyclic polymer precursor can be cyclized and the polymerization reaction of the heterocyclic polymer precursor can be carried out, thereby achieving a higher degree of heat resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal free radical polymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % relative to the total solid content of the curable resin composition of the present invention. The thermal free radical polymerization initiator may be contained in one type or in two or more types. When two or more thermal free radical polymerization initiators are contained, the total amount thereof is preferably within the above range.

<Polymerizable compound> [Free radical polymerizable compound] The curable resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a free radical polymerizable compound can be used. A free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. can be cited. The free radical polymerizable group is preferably a (meth)acryloyl group.

The number of radical polymerizable groups possessed by the radical polymerizable compound may be one or more than two. It is preferred that the radical polymerizable compound possess two or more radical polymerizable groups, and more preferably possesses three or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

The molecular weight of the radical polymerizable compound 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 radical polymerizable compound is preferably 100 or more.

From the viewpoint of developing properties, the curable resin composition of the present invention preferably contains at least one radically polymerizable compound having two or more radical polymerizable groups, and more preferably contains at least one radically polymerizable compound having three or more functional groups. In addition, it may be a mixture of a radically polymerizable compound having two or more functional groups and a radically polymerizable compound having three or more functional groups. For example, the number of functional groups of a polymerizable monomer having two or more functional groups means that the number of radically polymerizable groups in one molecule is two or more.

Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, and thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, as another example, instead of the above-mentioned unsaturated carboxylic acids, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can be used. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

In addition, the radical polymerizable compound is preferably a compound having a boiling point of 100°C or higher under 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 (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylate. Compounds of the present invention, (meth)acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

Furthermore, as preferred radical polymerizable compounds other than the above, 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, etc., or cardo resins can also be used.

Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing a perfluoroalkyl group described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photocurable 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 JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

In addition, the following compounds described as formula (1) and formula (2) together with their specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into this specification.

As the radical polymerizable compound, 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.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. The oligomer type of the above can also be used.

As commercially available products of the radical polymerizable compound, for example, there can be cited SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy chains, urethane 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, UA-7200 (manufactured by Shin-Nakamura Chemical 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.

As free radical polymerizable compounds, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those 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 are also preferred. Furthermore, as the radical polymerizable compound, a compound having an amino structure or a sulfide structure in the molecule 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 polymerizable compound may be a free radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical polymerizable compounds having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are more preferred. Particularly preferred free radical polymerizable compounds having acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides are compounds in which the aliphatic polyhydroxy compounds are neopentyl triol and/or dipentyl triol. As commercially available products, for example, as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. can be cited.

The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. As long as the acid value of the radical polymerizable compound is within the above range, the operability in production is excellent, and further the developing property is excellent. In addition, the polymerizability is also good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of suppressing warping accompanying control of elastic modulus of the cured film, the curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound. As the monofunctional free radical polymerizable compound, (meth)acrylic acid derivatives such as 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, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As the monofunctional free radical polymerizable compound, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

[Polymerizable compounds other than the above-mentioned free radical polymerizable compounds] The curable resin composition of the present invention may also contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; cyclohexane compounds; and benzophenone compounds.

-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group- As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.

[Chemical formula 27] (In the formula, t represents an integer of 1 to 20, R ¹⁰⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ¹⁰⁵ represents a group represented by -OR ¹⁰⁶ or -OCO-R ¹⁰⁷ , R ¹⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ¹⁰⁷ represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 28] (In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , R ⁴⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 29] (In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (these trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (these trade names, manufactured by Sanwa Chemical Co., Ltd.).

-Epoxy compound (compound having epoxy group)- As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy groups undergo crosslinking reaction below 200°C, and since dehydration reaction from crosslinking does not occur, it is not easy to cause film shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the modulus of elasticity and can suppress warping. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EPICLON (registered trademark) EXA-859CRP (trade name, manufactured by DIC Corporation), EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above trade names, manufactured by ADEKA CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warping and having excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

-Oxycyclobutane compounds (compounds having an oxycyclobutyl group)- As oxycyclobutane compounds, compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester, etc. can be cited. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used alone or in combination of two or more.

-Benzotriazole compounds (compounds having polybenzotriazole groups)- Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone (the above trade names, manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

When a polymerizable compound is contained, its content is preferably greater than 0 mass % and less than 60 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

The other polymerizable compounds may be used alone or in combination of two or more. When two or more are used simultaneously, it is preferred that the total amount thereof be within the above range.

<Solvent> The curable resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfones, and amides.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (for example, methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (for example, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (for example, methyl 3-alkoxy propionate, ethyl 3-alkoxy propionate, etc. (for example, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-methoxy propionate, etc.) 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like.

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, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. can be cited as preferred ones.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferred.

Preferred examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

As the sulfoxides, for example, dimethyl sulfoxide is preferably mentioned.

As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and the like.

Regarding the solvent, from the viewpoint of improving the properties of the coated surface, a mixture of two or more solvents is also preferred.

In the present invention, it is preferred to use a solvent selected from 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, or a mixed solvent consisting of two or more of the above. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously.

Regarding the content of the solvent, from the viewpoint of coating properties, it is preferably set to 5 to 80 mass % of the total solid content concentration of the curable resin composition of the present invention, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 40 to 70 mass %. The content of the solvent can be adjusted according to the desired thickness and coating method.

The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount of the solvents is within the above range.

<Migration inhibitor> The curable resin composition of the present invention preferably further comprises a migration inhibitor. By comprising the migration inhibitor, it is possible to effectively inhibit metal ions originating from the metal layer (metal wiring) from migrating into the curable resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, phenazine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

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

[Chemical formula 30]

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

The migration inhibitor may be one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferred that the total amount thereof is within the above range.

<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, oligol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenylnaphthalene, etc. can be preferably used. Amine, ethylenediaminetetraacetic 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-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

Furthermore, the following compounds (Me is methyl group) can also be used.

[Chemical formula 31]

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % based on the total solid content of the curable resin composition of the present invention.

The polymerization inhibitor may be one or more. When there are two or more polymerization inhibitors, it is preferred that the total amount of the polymerization inhibitors is within the above range.

<Metal Adhesion Improver> The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of the metal adhesion improver include silane coupling agents.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 32]

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfides described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the heterocyclic polymer precursor. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total is within the above range.

<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed within the scope that does not impair the effects of the present invention, such as thermal acid generators, sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are formulated, it is preferred that the total amount thereof be set to 3% by mass or less of the solid content of the composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal alkali generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat, etc. Thereby, the thermal alkali generator, the thermal radical polymerization initiator, and the photoradical polymerization initiator induce chemical changes and decompose to generate free radicals, acids, or bases. For the details of the sensitizer, reference can be made to the description of the sensitizing dye described in paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, and the contents are incorporated into this specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass % relative to the total solid content concentration of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent] The curable 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. As chain transfer agents, for example, a group of compounds having SH, PH, SiH and GeH in the molecule is used. These compounds generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the curable 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 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content concentration of the curable resin composition of the present invention. The chain transfer agent may be only one type or may be two or more types. When there are two or more types of chain transfer agents, the total range thereof is preferably within the above range.

[Surfactant] From the perspective of further improving the coating properties, various surfactants can be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content of each repeating unit (molar %), and the parentheses representing the repeating units of the side chains represent the number of repetitions of each repeating unit. [Chemical Formula 33] Furthermore, the surfactant may include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total range thereof is preferably within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to the curable resin composition of the present invention and concentrated on the surface of the composition during the drying process after coating.

Furthermore, the higher fatty acid derivatives may also include compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more kinds of higher fatty acid derivatives, the total range is preferably within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5 mass %, more preferably less than 1 mass %, and even more preferably less than 0.6 mass %.

From the viewpoint of insulation, the metal content of the hardening resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities accidentally contained in the hardening resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the hardening resin composition of the present invention, filtering the raw material constituting the hardening resin composition of the present invention through a filter, lining the inside of a device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

In view of the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the curable resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the content of halogen atoms in the form of halogen ions 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 of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges, respectively.

As a container for storing the curable resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resins or a bottle having a seven-layer structure of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Preparation of composition> The curable 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 performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as garbage or particles in the composition, it is preferred to perform filtering using a filter. Preferably, the pore size of the filter is 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. Preferably, the material of the filter is polytetrafluoroethylene, polyethylene or nylon. The filter can be pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. Furthermore, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. Furthermore, filtering can be performed after pressurization. When filtering is performed after pressurization, the pressure of pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtering using a filter, impurity removal treatment using an adsorbent can also be performed. Filtering using a filter and impurity removal treatment using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

<Use of the composition> The curable resin composition of the present invention is preferably used to form an interlayer insulating film for a redistribution layer. In addition, it can also be used to form an insulating film or a stress buffer film for a semiconductor device.

(Curing film, laminate, semiconductor device, and method for manufacturing the same) Next, the curing film, laminate, semiconductor device, and method for manufacturing the same are described.

The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, or 1 μm or more, and the upper limit can be set to 100 μm or less, or 30 μm or less.

The cured film of the present invention can be laminated in 2 or more layers, and further laminated in 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes 2 or more cured films, and preferably includes a metal layer between any of the cured films. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), or insulating films for actual mounting purposes such as those described above that are patterned by etching. For such applications, for example, reference can be made to Science & Technology Co., Ltd., “Advanced Functionality and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, “The Fundamentals and Development of Polyimide Materials”, November 2011, and Japan Polyimide and Aromatic Polymer Research Society, “The Latest Fundamentals and Applications of Polyimide”, NTS, August 2010.

Furthermore, the cured film of the present invention can also be used in the production of offset printing plates or screen printing plates, the use of molded parts, the production of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming process of applying the curable resin composition of the present invention to a substrate to form a film. Furthermore, the method for producing a cured film of the present invention preferably includes the above-mentioned film forming process and further includes a heating process of decomposing the compound represented by the above-mentioned formula (1-1) by heating the above-mentioned film. Specifically, the process including the following (a) to (d) is also preferred. (a) A film forming process of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (b) After the film forming process, an exposure process of exposing the film (c) A developing process of developing the exposed film (d) A heating process of decomposing the compound represented by the above formula (1-1) by heating the developed film The resin layer cured by exposure can be further cured by heating in the above heating process. In the heating process, for example, the compound represented by the above formula (1-1) is decomposed to obtain sufficient curability.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. The method for manufacturing a laminated body of the present embodiment forms a cured film according to the above-mentioned method for manufacturing a cured film, and then performs process (a) or processes (a) to (c), or processes (a) to (d) again after forming the cured film. In particular, it is preferred to perform the above-mentioned processes multiple times, for example 2 to 5 times (that is, 3 to 6 times in total) in sequence. By laminating the cured film in this way, a laminated body can be formed. In the present invention, it is preferred to provide a metal layer on a portion where a cured film is provided, between the cured films, or in both. In addition, in the manufacture of the laminate, it is not necessary to repeat all of the processes (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times. <Film-forming process (layer-forming process)> The manufacturing method of the preferred embodiment of the present invention includes a film-forming process (layer-forming process) of applying a curable resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. 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, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, and electrode plates of plasma display panels (PDP). In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. In addition, as a substrate, for example, a plate-shaped substrate (substrate) is used.

Furthermore, when a curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

As a method of applying the curable resin composition to the base material, coating is preferred.

Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of thickness uniformity of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred, and for a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, a method of transferring a coating film formed by applying the above-mentioned applying method to a pseudo support body in advance can also be applied. Regarding the transfer method, in the present invention, 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 can also be preferably used.

<Drying process> The manufacturing method of the present invention may further include a drying process for removing the solvent after forming the above-mentioned film (hardening resin composition layer) and after the film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. The drying time is exemplified as 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

<Exposure process> The manufacturing method of the present invention may include an exposure process for exposing the above-mentioned film (hardening resin composition layer). The exposure amount is not particularly limited as long as it can harden the hardening resin composition. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , in terms of exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, with 240 to 550 nm being the best.

Regarding exposure wavelength, if described in terms of its relationship with the light source, the following examples can be cited: (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beams, etc. The curable resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays. This can provide a particularly high exposure sensitivity.

<Development process> The manufacturing method of the present invention may include a development process for developing the exposed film (hardening resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed. There is no particular limitation on the development method as long as the desired pattern can be formed. For example, a development method such as coating, spraying, immersion, and ultrasonic wave can be used.

Development is performed using a developer. As long as the developer can remove the unexposed portion (non-exposed portion), it can be used without particular limitation. The developer preferably contains an organic solvent, and more preferably contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula into ChemBioDraw.

As for the organic solvent, examples of the esters include 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 alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.) ), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (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, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 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 Examples of the solvent include acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and examples of ketones include preferably methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like; and examples of aromatic hydrocarbons include preferably toluene, xylene, anisole, limonene, and the like; and examples of sulfoxides include preferably dimethyl sulfoxide.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.

Preferably, 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more of the developer is an organic solvent, and even more preferably 90% by mass or more of the developer is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing process is not particularly limited, but the developing process can usually be performed at 20 to 40°C.

After the treatment with the developer, rinsing can be performed. It is preferred that the rinsing be performed with a solvent different from the developer. For example, the solvent included in the curable resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

<Heating process> The manufacturing method of the present invention preferably includes a process (heating process) of decomposing the compound represented by the above formula (1-1) by heating the above film. It is preferred to include a heating process after the film formation process (layer formation process), drying process and development process. In the heating process, for example, a base is generated by decomposing the compound represented by the above formula (1-1), and a cyclization reaction of the heterocyclic polymer precursor is carried out. In addition, although the composition of the present invention may contain a free radical polymerizing compound other than the heterocyclic polymer precursor, the curing of the free radical polymerizing compound other than the unreacted heterocyclic polymer precursor can also be carried out in the process. As the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is further preferred, 150°C or higher is further preferred, 160°C or higher is further preferred, and 170°C or higher is further preferred. As the upper limit, 500°C or lower is preferred, 450°C or lower is more preferred, 350°C or lower is further preferred, 250°C or lower is further preferred, and 220°C or lower is further preferred.

Regarding heating, it is preferred that the heating be performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to ensure productivity while preventing excessive volatile amines, and by setting the heating rate to 12°C/min or less, it is possible to alleviate the residual stress of the cured film.

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 process of heating to the maximum heating temperature. For example, when a curable resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is uncertain, but it is believed that the acetylene groups of the heterocyclic polymer precursor between the layers undergo crosslinking reaction by setting the temperature to this level.

Heating can be performed in stages. For example, the pre-treatment process can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pre-treatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. The properties of the membrane can be improved by such pre-treatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a process of two or more stages, for example, pretreatment process 1 can be carried out in the range of 100 to 150°C, and then pretreatment process 2 can be carried out in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/minute.

Regarding the heating process, it is preferred to conduct the process in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon to prevent the decomposition of the heterocyclic polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<Metal layer forming process> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the film (hardening resin composition layer) after development treatment.

The metal layer is not particularly limited, and any existing metal can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further 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 Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest wall portion, and more preferably 1 to 10 μm. <Layering process> The manufacturing method of the present invention also preferably includes a layering process.

The lamination process includes a series of processes including (a) a film forming process (layer forming process), (b) an exposure process, (c) a developing process, and (d) a heating process, which are sequentially performed again on the surface of the hardened film (resin layer) or the metal layer. Among them, it is possible to have a mode in which only the film forming process (a) is repeated. In addition, it is also possible to have a mode in which the heating process (d) is performed at the end or in the middle of the lamination. That is, it is also possible to have a mode in which the processes (a) to (c) are repeated a specified number of times, and then the heating (d) is performed, thereby hardening the hardening resin composition layer to be laminated. Furthermore, the (c) developing process may include the (e) metal layer forming process, and the heating in (d) may be performed each time, or may be performed collectively after a predetermined number of layering processes. It is beyond doubt that the layering process may also appropriately include the above-mentioned drying process and heating process.

When the lamination process is further performed after the lamination process, a surface activation process may be further performed after the heating process, after the exposure process, or after the metal layer forming process. Plasma treatment is exemplified as the surface activation process.

The above-mentioned lamination process is preferably performed 2 to 5 times, and more preferably performed 3 to 5 times.

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, wherein the number of resin layers is 3 or more and 7 or less is preferred, and a structure of 3 or more and 5 or less is more preferred.

In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the hardening resin composition in a manner of covering the metal layer. Specifically, it is possible to cite an embodiment of sequentially repeating (a) a film forming process, (b) an exposure process, (c) a developing process, (e) a metal layer forming process, and (d) a heating process, or sequentially repeating (a) a film forming process, (b) an exposure process, (c) a developing process, and (e) a metal layer forming process, and then collectively providing (d) a heating process at the end or in the middle. By alternately performing the lamination process of the hardening resin composition layer (resin layer) and the metal layer forming process, the hardening resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device using the curable resin composition of the present invention in the formation of an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Publication No. 2016-027357, and the contents are incorporated into this specification.

(Thermoalkali generator) The thermoalkali generator of the present invention is a thermoalkali generator represented by the following formula (1-2). [Chemical formula 34] In formula (1-2), R ²¹ and R ²² each independently represent a monovalent organic group, L ²¹ represents a divalent linking group, the atoms in the bonding positions at both ends of L ²¹ are carbon atoms, and R ²³ represents a hydrogen atom or a monovalent organic group.

R ²¹ , R ²² and R ²³ in formula (1-2) have the same meanings as R ¹ , R ² and R ³ in formula (1-1), respectively, and preferably the same meanings as R 1 , R 2 and R 3 in formula (1-1). L ²¹ in formula (1-2) has the same meanings as L 1 in formula (1-1), except that the atoms at the bonding positions at both ends are limited to carbon atoms, and preferably the same meanings as L ¹ in formula (1-1).

<Application> The application of the thermal alkali generator of the present invention is not particularly limited. For example, by using it in combination with the above-mentioned heterocyclic polymer precursor, it can constitute a curable resin composition. In addition, it is believed that the thermal alkali generator of the present invention is not easy to decompose at room temperature, and the alkali generation efficiency when heated is excellent. Therefore, it is believed that it is advantageous to use the thermal alkali generator of the present invention instead of the known thermal alkali generator in various applications using the known thermal alkali generator or to use the thermal alkali generator of the present invention in combination with the known thermal alkali generator. [Example]

The present invention is further described in detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the main purpose 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 based on mass.

<Synthesis Example 1> [Synthesis of a polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether and benzyl alcohol (A-1: a polyimide precursor having no free radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 mL of N-methylpyrrolidone and dried using a molecular sieve. The suspension was heated at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while the temperature was maintained at -10±4°C. The viscosity increased during the addition of SOCl _2. After diluting 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 to 0°C over 20 minutes. Next, after the reaction mixture was reacted at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical Formula 35]

<Synthesis Example 2> [Synthesis of a polyimide precursor derived from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: a polyimide precursor having a radical polymerizable group)] 14.06 g (64.5 mmol) of pyromellitic acid dianhydride (dried 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 (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. [Chemical Formula 36]

<Synthesis Example 3> [Synthesis of a polyimide precursor (A-3: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (stirred 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 were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 18,000. [Chemical Formula 37]

<Synthesis Example 4> [Synthesis of a polyimide precursor (A-4: a polyimide precursor having a radical polymerizable group) derived from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (o-tolidine) and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (stirred 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 were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and a polyimide precursor was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the polyimide precursor was 19,000. [Chemical Formula 38]

<Synthesis Example 5> [Synthesis of polybenzoxazole precursor (A-5) derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydiphenylformyl chloride] 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone and stirred to dissolve. Then, 11.21 g of 4,4'-oxydiphenylformyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5000 rpm for 15 minutes. The polybenzoxazole precursor was removed by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Then, the obtained polybenzoxazole precursor was dried at 45°C for 3 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor was 15,000. [Chemical Formula 39]

<Synthesis Example 6> [Synthesis of Compounds B-1 to B-18] Compounds B-1 to B-18 were synthesized according to the method described in Organic Chemistry International (2014), 576715/1-576715/10, page 10.

<Synthesis Example 7> [Synthesis of a polyimide precursor derived from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-6: a polyimide precursor having a free radical polymerizable group)] 155.1 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a 2-liter separation flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction was terminated, the mixture was cooled to room temperature and then left to stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour. Thereafter, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered and vacuum dried to obtain a powdered polymer A-6. The weight average molecular weight (Mw) of the polymer A-6 was measured to be 20,000.

<Synthesis Example 8> [Synthesis of a polyimide precursor derived from 3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-7: a polyimide precursor having a free radical polymerizable group)] In Synthesis Example 7, except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic anhydride, a polymer A-7 was obtained by reacting in the same manner as described in Synthesis Example 7. The weight average molecular weight (Mw) of the polymer A-7 was measured to be 22,000.

<Examples 1 to 40 and Comparative Examples C1 and C2> In each of the examples and comparative examples, the components listed in Table 1 or Table 2 below were mixed to obtain each hardening resin composition. The hardening resin composition obtained was filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.45 μm. In Table 1 or Table 2, the value in the "mass parts" column indicates the content (mass parts) of each component. In Table 1 or Table 2, the entry "-" indicates that the component is not contained.

[Table 1] Hardening resin composition Heterocyclic polymer precursor The compound represented by formula (1) Photoradical polymerization initiator Free radical polymerizable compounds Polymerization inhibitor Migration inhibitors Metal Adhesion Improver Solvent Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality 1 A-1 31.5 B-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 2 A-2 31.5 B-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 3 A-3 31.5 B-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 4 A-4 31.5 B-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 5 A-5 31.5 B-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 60 I-2 0 6 A-3 31.5 B-2 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 7 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 8 A-3 31.5 B-4 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 9 A-3 31.5 B-5 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 10 A-3 31.5 B-6 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 11 A-3 31.5 B-7 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 12 A-3 31.5 B-8 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 13 A-3 31.5 B-9 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 14 A-3 31.5 B-10 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 15 A-3 31.5 B-11 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 16 A-3 31.5 B-12 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 17 A-3 31.5 B-13 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 18 A-3 31.5 B-14 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 19 A-3 31.5 B-15 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 20 A-3 31.5 B-16 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 twenty one A-3 31.5 B-17 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 twenty two A-3 31.5 B-18 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15

[Table 2] Hardening resin composition Heterocyclic polymer precursor The compound represented by formula (1) Photoradical polymerization initiator Free radical polymerizable compounds Polymerization inhibitor Migration inhibitors Metal Adhesion Improver Solvent Additives Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality Kind Quality twenty three A-3 32.0 B-3 0.002 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - twenty four A-3 32.0 B-3 0.030 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 25 A-3 31.0 B-3 1.0 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 26 A-3 29.5 B-3 2.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 27 A-3 31.5 B-3 0.5 C-2 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 28 A-3 31.5 B-3 0.5 C-3 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 29 A-3 31.5 B-3 0.5 C-1 1.3 D-2 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 30 A-3 31.5 B-3 0.5 C-1 1.3 D-3 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 31 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-2 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 32 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-3 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - 33 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-2 0.1 G-1 0.6 I-1 45 I-2 15 - - 34 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-3 0.1 G-1 0.6 I-1 45 I-2 15 - - 35 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-4 0.1 G-1 0.6 I-1 45 I-2 15 - - 36 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-2 0.6 I-1 45 I-2 15 - - 37 A-3 31.5 B-3 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-3 0.6 I-1 45 I-2 15 - - 38 A-3 30.4 B-2 0.3 C-1 1.1 D-1 5.3 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - B-8 0.3 - - 39 A-3 31.5 B-2 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-3 60 - - - - 40 A-6 17.2 B-1 0.5 C-1 0.7 D-2 2.7 E-4 0.02 - - G-1 0.2 I-3 48 I-4 12 H-1 1.4 A-7 17.2 G-4 0.2 C1 A-1 31.5 RB-1 0.5 C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - - C2 A-1 32.0 - - C-1 1.3 D-1 5.9 E-1 0.1 F-1 0.1 G-1 0.6 I-1 45 I-2 15 - -

The details of each component listed in Table 1 or Table 2 are as follows. [Heterocyclic polymer precursor] ·A-1 to A-5: A-1 to A-5 synthesized as described above [Compounds represented by formula (1-1)] ·B-1 to B-18: Exemplary compounds B-1 to B-18 described above ·Compound RB-1 for comparison: Compound represented by the following formula (RB-1) [Chemical formula 40] [Photoradical 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) [Radical polymerizable compound] ·D-1: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)) ·D-2: SR-209 (manufactured by Sartomer Company, Inc., the following compound) [Chemical formula 41] ·D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate) [Polymerization inhibitor] ·E-1: 2,6-di-tert-butyl-4-methylphenol (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.) ·E-4: 2-Nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) (Migration inhibitor) ·F-1 to F-4: Compounds represented by the following formulas (F-1) to (F-4) [Chemical Formula 42] [Metal Adhesion Improver] G-1 to G-3: Compounds represented by the following formulas (G-1) to (G-4) [Chemical Formula 43] [Solvent] I-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) I-2: Dimethyl sulfoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation) I-3: N-methyl-2-pyrrolidone (manufactured by Ashland Co., Ltd.) I-4: Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Additive] H-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation> In each embodiment and comparative example, the curable resin composition described in Table 3 was used to evaluate the storage stability, elongation at break, and adhesion. The details of the evaluation method in each evaluation are described below.

[Storage stability] In each of the examples and comparative examples, the viscosity (0 day) of each curable resin composition was measured using an E-type viscometer. After the curable resin composition was allowed to stand at 25°C for 14 days in a light-shielded sealed container, the viscosity (14 days) of each curable resin composition after the standing was measured again using an E-type viscometer. In each of the examples and comparative examples, the viscosity variation rate was calculated using the values of the above viscosity (0 day) and the above viscosity (14 days) according to the following formula. The lower the viscosity variation rate, the higher the storage stability. Evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in the column "Storage stability" in Table 3.

Viscosity change rate (%) = |100×{1-(viscosity (14 days)/viscosity (0 days))}| The viscosity was measured at 25°C and in accordance with JIS Z 8803:2011. -Evaluation criteria- A: Viscosity change rate is 5% or less. B: Viscosity change rate exceeds 5% and is less than 20%. C: Viscosity change rate exceeds 20%.

[Elongation at break] In each of the embodiments and comparative examples, each hardening resin composition was applied (coated) on a wafer in a layered manner by spin coating, thereby forming a hardening resin composition layer. The silicon wafer to which the hardening resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes, thereby forming a hardening resin composition layer with a uniform thickness of 20 μm on the silicon wafer. The hardening resin composition layer on the wafer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C). The exposed curable resin composition layer (resin layer) was heated at a rate of 10°C/min in a nitrogen atmosphere, and after reaching 180°C, the temperature was maintained for 3 hours. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.

The elongation at break of the resin film 1 was measured in accordance with JIS-K6251:2017 using a tensile tester (TENSILON) at a crosshead speed of 300 mm/min, a sample width of 10 mm, and a sample length of 50 mm in the longitudinal and width directions of the film at 25°C and a relative humidity (RH) of 65%. The elongation at break was calculated by _Eb (%) = ( _Lb - _L0 ) / _L0 × 100 ( _Eb : elongation at break, _L0 : length of the test piece before the test, _Lb : length of the test piece when the test piece has been cut). In the evaluation, the elongation at break in the longitudinal direction was measured 5 times, and the average value was used. The evaluation was conducted according to the following evaluation criteria. The evaluation results are recorded in the "Elongation at break" column of Table 3. -Evaluation criteria- A: Elongation at break exceeds 60%. B: Elongation at break exceeds 55% and is less than 60%. C: Elongation at break exceeds 40% and is less than 55%. D: Elongation at break is less than 40%.

[Adhesion (Copper Adhesion)] In each of the Examples and Comparative Examples, each hardening resin composition was applied to a copper substrate in a layered manner by spin coating, and dried at 100°C for 5 minutes to form a hardening resin composition layer with a film thickness of 20 μm. The obtained copper substrate to which the hardening resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes to form a hardening resin composition layer with a uniform thickness of 20 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C), a 100μm square mask with a square non-masking portion was used to expose the curable resin composition layer on the copper substrate at an exposure energy of 500mJ/ ^cm2 , and then developed with cyclopentanone for 60 seconds to obtain a 100μm square resin layer. Furthermore, in a nitrogen atmosphere, the temperature was raised at a rate of 10℃/min, and after reaching 180℃, this temperature was maintained for 3 hours.

The shear force of a 100μm square resin layer on a copper substrate was measured using an adhesion tester (manufactured by XYZTEC, CondorSigma) at 25°C and 65% relative humidity (RH). The greater the shear force, the greater the adhesion and the better the result. The evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion" column of Table 3. -Evaluation Criteria- A: The shear force exceeds 40gf. B: The shear force exceeds 25gf and is less than 40gf. C: The shear force is less than 25gf. Among them, 1gf is 9.80665× ^10-3 N (Newton).

[Table 3] Hardening resin composition Preserve stability Elongation at break Tightness Hardening resin composition Preserve stability Elongation at break Tightness Embodiment 1 1 A B B Embodiment 23 twenty three A C A Embodiment 2 2 A B B Embodiment 24 twenty four A B A Embodiment 3 3 A A A Embodiment 25 25 A A A Embodiment 4 4 A A A Embodiment 26 26 B A B Embodiment 5 5 A B B Embodiment 27 27 A A A Embodiment 6 6 A A B Embodiment 28 28 A A A Embodiment 7 7 A A A Embodiment 29 29 A A A Embodiment 8 8 A A A Embodiment 30 30 A A A Embodiment 9 9 A A B Embodiment 31 31 A A A Embodiment 10 10 A A A Embodiment 32 32 A A A Embodiment 11 11 A C A Embodiment 33 33 A A A Embodiment 12 12 A A A Embodiment 34 34 A A A Embodiment 13 13 A C A Embodiment 35 35 A A B Embodiment 14 14 A A A Embodiment 36 36 A A A Embodiment 15 15 A C A Embodiment 37 37 A A A Embodiment 16 16 A B A Embodiment 38 38 A A A Embodiment 17 17 A C B Embodiment 39 39 A A A Embodiment 18 18 A C B Embodiment 40 40 A A A Embodiment 19 19 B B A Comparative example 1 C1 C B B Embodiment 20 20 A A A Comparative example 2 C2 A D C Embodiment 21 twenty one A A A Embodiment 22 twenty two A A A

From the above results, it can be seen that the curable resin composition of the present invention containing the heterocyclic polymer precursor and the compound represented by formula (1-1) has excellent storage stability and the obtained cured film has excellent elongation at break. The curable resin composition of Comparative Example 1 does not contain the compound represented by formula (1-1), but contains the compound represented by formula (RB-1) as a thermal alkali generator. It can be seen that the curable resin composition of Comparative Example 1 has poor storage stability. The curable resin composition of Comparative Example 2 does not contain the compound represented by formula (1-1). It can be seen that the curable resin composition of Comparative Example 2 has poor elongation at break.

<Example 101> The curable resin composition described in Example 1 was applied to the surface of the resin substrate on which the copper thin layer was formed by spin coating, and dried at 100°C for 5 minutes to form a curable resin composition layer with a film thickness of 20μm, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, the pattern was obtained by developing with cyclopentanone for 30 seconds and rinsing with PGMEA for 20 seconds. Then, the interlayer insulating film for the redistribution layer was formed by heating at 230°C for 3 hours. The insulation properties of the interlayer insulating film for the redistribution layer are excellent. In addition, the semiconductor device was manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without

without.

Claims (12)

A curable resin composition comprising: a heterocyclic polymer precursor selected from polyimide precursors and polybenzoic acid precursors;

At least one precursor of the group consisting of azole precursors; and a compound represented by the following formula (1-1),

In formula (1-1), ^R1 and ^R2 each independently represent a monovalent alkyl group, ^L1 represents a 1,2-ethylene ethyl group, a 1,3-propanediyl group, a 1,2-cyclohexanediyl group, a cis-ethylene vinyl group, a 1,2-phenylene methylene group or a 1,2-ethoxy-1,2-ethylene vinyl group, ^R3 represents a monovalent alkyl group or an aryl group, ^R1 and ^R2 may be bonded to form a ring structure, and the molecular weight of the compound represented by the aforementioned formula (1-1) is 100 or more and 2,000 or less. The curable resin composition as described in claim 1 further comprises a photo-radical polymerization initiator and a radical polymerizable compound. The curable resin composition as described in claim 1 contains a polyimide precursor as a precursor of the aforementioned heterocyclic polymer. The curable resin composition as claimed in claim 3, wherein the polyimide precursor has a repeating unit represented by the following formula (1):

In formula (1), ^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. The curable resin composition as described in claim 4, wherein at least one of R ¹¹³ and R ¹¹⁴ in the above formula (1) contains a free radical polymerizable group. The curable resin composition as described in claim 1 is used to form an interlayer insulating film for a redistribution layer. A cured film formed by curing a curable resin composition as described in any one of claims 1 to 6. A laminate comprising two or more layers of the hardened films as described in claim 7, and a metal layer between any of the hardened films. A method for manufacturing a cured film, comprising a film forming process of applying a curable resin composition as described in any one of claim 1 to claim 6 to a substrate to form a film. The method for manufacturing a cured film as described in claim 9 further includes a heating process for decomposing the compound represented by the aforementioned formula (1-1) by heating the aforementioned film. A semiconductor device comprising a hardened film as described in claim 7 or a laminate as described in claim 8. A hot alkali generator, which is represented by the following formula (1-2), wherein

In formula (1-2), R ²¹ and R ²² each independently represent a monovalent alkyl group, L ²¹ represents a 1,2-ethylene group, a 1,3-propanediyl group, a 1,2-cyclohexanediyl group, a cis-ethylenediyl group, a 1,2-phenylenemethylene group or a 1,2-ethoxy-1,2-ethylene group, R ²³ represents a monovalent alkyl group or an aryl group, and the molecular weight of the thermal alkali generator represented by the aforementioned formula (1-2) is 100 or more and 2,000 or less.