TWI877051B - Resin - Google Patents

Abstract

The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, and a new resin having a specific structure, wherein the curable resin composition includes a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and a polymerization initiator.

Description

Resin

The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device and a resin.

Since polyimide has excellent heat resistance and insulation, it is suitable for various uses. The above uses are not particularly limited. If we take semiconductor devices for actual mounting as an example, we can cite the use as a material or protective film for insulating films or sealing materials. In addition, it can also be used as a base film or cover film (COVERLAY) of a flexible substrate.

For example, in the above-mentioned applications, polyimide is sometimes used in the form of a curable resin composition containing polyimide, and sometimes in the form of a curable resin composition containing a polyimide precursor. The above-mentioned precursor is cyclized by heating, etc. to become a resin of polyimide. Such curable resin compositions can be applied to substrates, etc. by known coating methods, etc., so it can be said that the adaptability in manufacturing is excellent, for example, the degree of freedom in designing the shape, size, and application position of the curable resin composition to be applied is high. In addition to the high performance of resins such as polyimide, this type of manufacturing adaptability is also excellent. There is an increasing expectation to expand the industrial application of curable resin compositions containing polyimide or polyimide precursors.

For example, Patent Document 1 describes a photosensitive resin composition comprising: a polyamine having a specific structure; a photopolymerizable compound; and a photopolymerization initiator.

[Patent Document 1] Japanese Patent Publication No. 2009-251451

It is desirable to provide a curable resin composition containing polyimide, in which the obtained cured film has excellent chemical resistance.

The purpose of one embodiment of the present invention is to provide a curable resin composition having excellent chemical resistance 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. In addition, the purpose of another embodiment of the present invention is to provide a new resin.

Representative embodiments of the present invention are described below. <1> A curable resin composition comprising a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2) and a polymerization initiator, [Chemical Formula 1] In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds, L ¹¹ represents a divalent linking group including a polymerizable group, In formula (1-2), R ²¹ is a tetravalent group having a plurality of amide bonds, L ²¹ represents a divalent group including a polymerizable group, and R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group. <2> The curable resin composition as described in <1>, wherein the resin has a repeating unit represented by the following formula (2-1) as a repeating unit represented by the above formula (1-1) or has a repeating unit represented by the following formula (2-2) as a repeating unit represented by the above formula (1-2), [Chemical Formula 2] In formula (2-1), ^X1 and ^X2 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^Y1 represents an organic group having 1 to 30 carbon atoms, ^Q1 represents an organic group having 1 to 30 carbon atoms, ^A1 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A2 represents a group containing a polymerizable group, ^R1 and ^R2 each independently represent a hydrogen atom or a monovalent organic group, n1 and n2 each independently represent an integer greater than 1, In formula (2-2), ^X3 and X4 represent an integer greater than 1. ^{R 4} each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, Y ² represents an organic group having 1 to 30 carbon atoms, Q ² represents an organic group having 1 to 30 carbon atoms, A ³ represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, A ⁴ represents a group containing a polymerizable group, R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, G ¹ and G ² each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer greater than 1. <3> The curable resin composition according to <2>, wherein ^X1 and ^X2 in the above formula (2-1) are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms, and ^X3 and ^X4 in the above formula (2-2) are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms. <4> The curable resin composition according to <2> or <3>, wherein ^Y1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Y2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group. <5> The curable resin composition according to any one of <2> to <4>, wherein ^Q1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Q2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group. <6> The curable resin composition as described in any one of <1> to <5>, further comprising a polymerizable compound. <7> The curable resin composition as described in <6>, further comprising a multifunctional polymerizable compound as the above-mentioned polymerizable compound. <8> The curable resin composition as described in any one of <1> to <7>, which is used to form an interlayer insulating film for a redistribution layer. <9> A cured film, which is formed by curing the curable resin composition as described in any one of <1> to <8>. <10> A laminate having two or more layers of the cured films as described in <9>, and having a metal layer between any of the above-mentioned cured films. <11> A method for producing a cured film, comprising: a film forming step, wherein the curable resin composition described in any one of <1> to <8> is applied to a substrate to form a film. <12> The method for producing a cured film as described in <11>, comprising the step of heating the film at 50 to 450°C. <13> A semiconductor device, comprising the cured film described in <9> or the laminate described in <10>. <14> A resin comprising at least one selected from the group consisting of a repeating unit represented by formula (2-1) and a repeating unit represented by formula (2-2). [Chemical Formula 3] In formula (2-1), ^X1 and ^X2 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^Y1 represents an organic group having 1 to 30 carbon atoms, ^Q1 represents an organic group having 1 to 30 carbon atoms, ^A1 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A2 represents a group containing a polymerizable group, ^R1 and ^R2 each independently represent a hydrogen atom or a monovalent organic group, and n1 and n2 each independently represent an integer greater than 1; In formula (2-2), ^X3 and X4 represent an integer greater than 1. ^{R 4} independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, Y ² represents an organic group having 1 to 30 carbon atoms, Q ² represents an organic group having 1 to 30 carbon atoms, A ³ represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, A ⁴ represents a group containing a polymerizable group, R ³ and R ⁴ independently represent a hydrogen atom or a monovalent organic group, G ¹ and G ² independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 independently represent an integer greater than 1. [Effects of the Invention]

According to one embodiment of the present invention, a curable resin composition having excellent chemical resistance 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 are provided. In addition, according to another embodiment of the present invention, a new resin 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 "～" sign indicates a range including the numerical values recorded before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only indicates an independent step, but also includes steps that cannot be clearly distinguished from other steps as long as the expected effect of the step 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, when simply described as "aliphatic group", "aliphatic alkyl group", "saturated aliphatic alkyl group", "alkyl group", "alkylene group", etc., unless otherwise specified, these groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl" includes straight chain alkyl groups, branched chain alkyl groups, cyclic alkyl groups, and alkyl groups represented by combinations thereof. In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used for exposure, the bright line spectrum of mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam and other actinic rays or radiation can be cited. 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 methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, the total solid content refers to the total mass of all components of the composition except the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components except the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as the column. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as the washing liquid. Also, unless otherwise specified, the detection in the GPC measurement is performed using a UV (ultraviolet) detector with a wavelength of 254nm. In this manual, when the positional relationship of each layer constituting the laminate is recorded as "upper" or "lower", it is sufficient as long as other layers exist on the upper or lower side of the layer serving as the reference among the multiple layers concerned. In other words, a third layer or a third element may be further sandwiched between the layer serving as the reference and the other layers mentioned above, and the layer serving as the reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction of stacking layers on a substrate is referred to as "up", or in the case of a curable resin composition layer, the direction from the substrate toward the curable resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of the up and down directions is for the convenience of explaining this specification, and in actual forms, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, as each component contained in a composition, the composition may also contain two or more compounds corresponding to the component. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this manual, the combination of the best state is the more preferred state.

(Hardening resin composition) The hardening resin composition of the present invention (hereinafter, referred to as "the composition of the present invention") comprises a resin having at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1-1) and repeating units represented by the following formula (1-2) and a polymerization initiator. Hereinafter, the resin having at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1-1) and repeating units represented by the following formula (1-2) is also referred to as a "specific resin". [Chemical Formula 4] In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds, and L ¹¹ represents a divalent linking group including a polymerizable group. In formula (1-2), R ²¹ is a tetravalent group having a plurality of amide bonds, L ²¹ represents a divalent group including a polymerizable group, and R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group. In the present specification, an amide bond refers to a structure represented by (-C(=O)NR-). The above R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aromatic alkyl group, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aromatic alkyl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom. In this specification, when simply described as "ester bond (-C (=O) O-)", "urethane bond (-OC (=O) NR-)", "amide bond", etc., the direction of the bond is not limited. The R in the urethane bond (-OC (=O) NR-) has the same meaning as the R in the amide bond, and the preferred embodiment is also the same.

The curable resin composition of the present invention is preferably a negative curable resin composition. A negative curable resin composition refers to a composition in which the unexposed portion (non-exposed portion) is removed by a developer when a layer formed by the curable resin composition is exposed. In addition, in the present invention, a repeating unit refers to the smallest of the constituent units that constitute the resin by repeated connection. That is, for example, a resin having a constituent unit obtained by bonding two repeating units represented by formula (1-2) is not a resin having a repeating unit obtained by bonding two repeating units represented by formula (1-2), but a resin having two repeating units represented by formula (1-2).

The cured film obtained from the curable resin composition of the present invention has excellent chemical resistance. The mechanism by which the above effect can be obtained is not yet clear, but it is speculated as follows.

The curable resin composition of the present invention includes a resin having a repeating unit represented by the above formula (1-1) (hereinafter also referred to as a "specific resin"). However, unlike the polyimide resin or polyimide precursor used in the past, the specific resin includes a plurality of amide bonds in R ¹¹ or R ²¹ in the formula (1-1) or (1-2), and includes a polymerizable group in L ¹¹ or L ^21. The amide bond has a high hydrogen bonding property, and therefore it is considered that the resin includes the plurality of amide bonds and generates interactions between resins or within the resin. It is speculated that in the cured film after curing, a high-density mesh structure is formed by the above-mentioned interaction and crosslinking based on polymerization of the polymerizable group contained in ^L11 or ^L21 close to the above-mentioned amide bond. It is considered that in the cured film having such a high-density mesh structure, it becomes difficult for chemicals to penetrate. Thus, it is speculated that according to the curable resin composition of the present invention, a cured film with excellent chemical resistance and suppressed chemical penetration can be obtained. It is considered that due to the excellent chemical resistance of the cured film, when, for example, another curable resin composition containing a solvent is applied to the cured film formed by curing the curable resin composition of the present invention and cured to produce a laminate, even if the cured film contacts a developer or other curable resin compositions, dissolution of the cured film is suppressed. It is considered that according to the present invention, a cured film can be obtained, which has suppressed solubility in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, or mixed solutions of the above polar solvents and the above alkaline aqueous solutions, and has excellent chemical resistance. Furthermore, it is speculated that, since the specific resin has a polymerizable group with high solvent solubility in ^L11 or ^L21 in Formula (1-1) or Formula (1-2), the permeability of the developer in the composition before polymerization is improved, so that a composition film (photosensitive film) with excellent developability is easily obtained.

Among them, Patent Document 1 does not describe or suggest a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by Formula (1-1) and a repeating unit represented by Formula (1-2). In addition, the curable resin composition in Patent Document 1 has a problem that the chemical resistance of the obtained cured film is low.

<Specific resin> The curable resin composition of the present invention contains a specific resin. The specific resin has at least one repeating unit selected from the group including the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2). The specific resin may have at least one repeating unit selected from the group including the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2) on the side chain, but it is preferred to have the above repeating unit on the main chain. In this specification, "main chain" refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" refers to the other bond chains.

[Repeating unit represented by formula (1-1)] -R ¹¹ - In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds. The amide bonds contained in R ¹¹ may be contained in the main chain of the specific resin or in the side chain of the specific resin, but from the viewpoint of drug resistance, it is preferably contained in the main chain of the specific resin. The number of amide bonds in R ¹¹ may be two or more, but 2 to 10 are preferred, 2 to 5 are more preferred, 2 to 4 are further preferred, two or three are particularly preferred, and two is the most preferred. R ¹¹ may be a tetravalent group, but preferably contains at least one group selected from the group consisting of aliphatic hydrocarbon groups and aromatic hydrocarbon groups and two or more amide bonds. From the viewpoint of developing properties, R ¹¹ is preferably a group containing an aromatic hydrocarbon group. From the viewpoint of chemical resistance, R ¹¹ is preferably a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxadiazole group, a hydroxymethyl group or an alkoxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred. The number of polymerizable groups contained in R ¹¹ is preferably one or more, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one. From the viewpoint of solubility in developer, R ¹¹ preferably has at least one group selected from the group consisting of aliphatic hydrocarbon groups and polyalkylene oxide groups as a substituent. As such substituents, groups represented by the formula (P-4) described below are preferred.

＜＜Formula (R-1)＞＞ Among them, R ¹¹ is preferably a group represented by the following formula (R-1). [Chemical Formula 5]

In formula (R-1), ^X1 and ^X2 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^L1 and ^L2 each independently represent a single bond or a divalent linking group, ^R1 and ^R2 each independently represent a hydrogen atom or a hydrocarbon group, ^L3 represents a divalent linking group, * each represents a bonding site to one of the two imide structures in formula (1-1), and # each represents a bonding site to the other of the above imide structures.

＜＜＜X ¹ and X ² ＞＞＞ In formula (R-1), X ¹ and X ² are each independently preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aliphatic cyclic group having 3 to 30 carbon atoms. As the above aromatic hydrocarbon group having 6 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred, an aromatic hydrocarbon group having 6 to 10 carbon atoms is further preferred, and a structure obtained by removing three hydrogen atoms from a benzene ring is further preferred. As the above aliphatic cyclic group having 3 to 30 carbon atoms, an aliphatic cyclic group having 4 to 20 carbon atoms is further preferred, an aliphatic cyclic group having 6 to 10 carbon atoms is further preferred, and a structure obtained by removing three hydrogen atoms from an aliphatic cyclic structure having a 6-membered ring structure is further preferred. The above-mentioned aliphatic cyclic group may be a saturated aliphatic cyclic group or an unsaturated aliphatic cyclic group, but a saturated aliphatic cyclic group is preferred. The above-mentioned aliphatic cyclic group may be an aliphatic alkyl cyclic group or an aliphatic heterocyclic group, but an aliphatic alkyl cyclic group is preferred. Among them, as the above-mentioned aliphatic cyclic group, a saturated aliphatic alkyl group is preferred. In the aromatic alkyl group or aliphatic cyclic group as ^X1 or ^X2 , it is preferred that the two * in ^X1 and the two # in ^X2 are present in adjacent positions in the aromatic alkyl group or aliphatic cyclic group. In this specification, two bonding sites exist at adjacent positions in a ring structure, which means that a ring member in the ring structure existing at one bonding site and a ring member in the ring structure existing at another bonding site are adjacent ring members in the ring structure. For example, when the ring structure is a benzene ring structure, the adjacent positions are adjacent positions.

The above ^X1 and ^X2 may have a substituent within a range that the effects of the present invention can be obtained. Examples of the substituent include an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aryloxy group, a halogenated alkyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, and a halogen atom.

＜＜＜L ¹ and L ² ＞＞＞ In formula (R-1), L ¹ and L ² are each independently a single bond, a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group obtained by bonding two or more of these groups, and a single bond is more preferred. As the above-mentioned "group obtained by bonding two or more of these groups", urea groups and the like are preferably exemplified. The above-mentioned ^RN represents a hydrogen atom or a alkyl group, and a hydrogen atom, an alkyl group or an aromatic alkyl group is more preferred, a hydrogen atom or an alkyl group is further preferred, and a hydrogen atom is particularly preferred. As the above-mentioned alkyl group, a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by such a bond is more preferred. In addition, the alkyl group in ^L1 and ^L2 may have a group containing a polymerizable group as a substituent. As the polymerizable group, the polymerizable group in ^R11 mentioned above can be cited. From the viewpoint of solubility in developer, the alkyl group in ^L1 and ^L2 may have a group containing at least one group selected from the group including an aliphatic alkyl group and a polyalkylene oxide group as a substituent. As these substituents, groups represented by the formula (P-4) described later are preferred.

In formula (R-1), ^R1 and ^R2 each independently represent a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

＜＜＜L ³ ＞＞＞ In formula (R-1), L ³ is preferably a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group obtained by bonding two or more of these groups. Preferably, the alkyl group or at least one alkyl group is bonded to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, and urea. The above-mentioned ^RN is as described above. As the above-mentioned alkyl group, a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by such a bond is more preferred. In addition, the alkyl group in L ³ may have a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic alkyl group, and a polyalkylene oxide group as a substituent. As the polymerizable group, the polymerizable group in the above-mentioned R ¹¹ can be cited. From the viewpoint of the chemical resistance of the obtained cured film, it is preferred to have a group containing at least a polymerizable group as a substituent. From the viewpoint of developer solubility, a substituent having at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkylene oxide group is preferred. As such a substituent, a group represented by the formula (P-4) described below is preferred. Moreover, as L ³ , a group represented by the formula (L-1) below is preferred. [Chemical Formula 6] In formula (L-1), ^Y1 represents an organic group having 1 to 30 carbon atoms, ^A1 represents a group comprising at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, n1 represents an integer greater than 1, * represents a bonding site to the nitrogen atom to which ^R1 in formula (R-1) is bonded, and # represents a bonding site to the nitrogen atom to which ^R2 in formula (R-1) is bonded.

In formula (L-1), ^Y1 is preferably a alkyl group or a group formed by at least one alkyl group bonding to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) _2- , and ^-NRN- . A structure formed by a alkyl group or at least one alkyl group bonding to an amide is preferably.

Furthermore, ^Y1 is preferably a group represented by the following formula (Y-1). [Chemical Formula 7] In formula (Y-1), ^RY1 , ^RY2 and ^RY3 each independently represent an organic group having 1 to 30 carbon atoms, ^Z1 and ^Z2 each independently represent an amide bond, a and b each independently represent an integer greater than 0, and at least one of ^RY1 , ^RY2 and ^RY3 in formula (Y-1) represents a bonding site with ^A1 in formula (L-1).

In formula (Y-1), ^RY1 , ^RY2 and ^RY3 are each independently preferably a group containing an aliphatic alkyl group or an aromatic alkyl group, and preferably a group containing an aromatic alkyl group. As the aliphatic alkyl group, an aliphatic alkyl group having 1 to 30 carbon atoms is preferred, and an aliphatic alkyl group having 2 to 20 carbon atoms is more preferred. As the aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, an aromatic alkyl group having 6 to 20 carbon atoms is more preferred, an aromatic alkyl group having 6 to 12 carbon atoms is further preferred, and an aromatic alkyl group having 6 carbon atoms is particularly preferred. Furthermore, R ^Y1 , R ^Y2 and R ^Y3 are each independently a structure represented by any one of the following formulas (Y1-1) to (Y1-4), preferably a structure represented by formula (Y1-3) or (Y1-4), and more preferably a structure represented by formula (Y1-3). In formulas (Y1-1) to (Y1-4), * represents a bonding site with other structures, and # represents a bonding site with A ¹ in formula (L-1) or a bonding site with a hydrogen atom. [Chemical Formula 8] In formula (Y1-1) or formula (Y1-2), L ^Y1 and L ^Y2 each independently represent an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and further preferably a methylene group. In formula (Y1-3) or formula (Y1-4), L ^Y4 each independently represent a single bond or a divalent hydrocarbon group, preferably a single bond. As the divalent hydrocarbon group, an alkylene group is preferred, more preferably an alkylene group having 1 to 10 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms. In formula (Y1-4), L ^Y3 is preferably a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHC(=O)-, or a group obtained by combining two or more of them. It is more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -S(=O) ₂ -. It is even more preferably a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -S(=O) ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -. In formula (Y1-3) or formula (Y1-4), n independently represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

In formula (Y-1), the amide bonds in ^Z1 and ^Z2 are independently the same as the amide bonds in ^R11 , and the preferred embodiments are also the same. In addition, the directions of the amide bonds in ^Z1 and ^Z2 are not particularly limited.

In formula (Y-1), a and b each independently represent an integer greater than or equal to 0, preferably an integer from 0 to 4, more preferably an integer from 0 to 2, further preferably 0 or 1, and particularly preferably 0.

In formula (L-1), ^A1 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkoxy group. As the polymerizable group, a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group or a hydroxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred. When ^A1 is a group containing a polymerizable group, the number of polymerizable groups contained in ^A1 is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one. A preferred embodiment in which ^A1 is a group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a polyalkylene group is as described as a substituent of ^L3 in the above formula (R-1).

When ^A1 contains a polymerizable group, the group represented by the following formula (P-1) is preferred. [Chemical Formula 9] In formula (P-1), L ¹ represents a single bond or an m+1 valent linking group, A ² represents a polymerizable group, m represents an integer greater than 1, and * represents a bonding site with Y ^1. In formula (P-1), L ¹ is preferably a single bond or a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group obtained by bonding two or more of these groups, and more preferably a single bond or a alkyl group, -O-, -C(=O)-, -NR ^N -, or a group obtained by bonding two or more of these groups. Examples of the above-mentioned "groups obtained by bonding two or more of these groups" include urea groups and the like. The above-mentioned ^RN represents a hydrogen atom or a alkyl group, and a hydrogen atom, an alkyl group or an aryl group is more preferred, a hydrogen atom or an alkyl group is further preferred, and a hydrogen atom is particularly preferred. As the alkyl group in the above-mentioned ^L1 , a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by such a bond is more preferred.

In formula (P-1), ^A2 is preferably vinyl, (meth)allyl, (meth)acrylamide, (meth)acryloxy, cis-butylenediamide, vinylphenyl, epoxy, cyclohexyl, hydroxymethyl or alkoxymethyl, and more preferably (meth)acryloxy, (meth)acrylamide, epoxy, hydroxymethyl or alkoxymethyl.

In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

Furthermore, ^A1 is preferably a group represented by the following formula (P-2) or formula (P-3). [Chemical Formula 10] In formula (P-2), A ² represents a polymerizable group, and * represents a bonding site with Y ^1. In formula (P-2), A ² has the same meaning as A ² in formula (P-1), and a preferred embodiment is also the same. In formula (P-3), A ² represents a polymerizable group, L ² represents a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, a carbonate bond, a urea group, or a group obtained by bonding two or more of these groups, Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond, a carbonate bond, or an amide bond, and * represents a bonding site with Y ^{1. RN} is as described above. In formula (P-3), A ² has the same meaning as A ² in formula (P-1), and the preferred embodiment is also the same. In formula (P-3), L ² is preferably a alkyl group, a (poly)alkoxyl group, or a group represented by a combination thereof, and a alkyl group is more preferred. In the present specification, a (poly)alkoxyl group represents an alkoxyl group or a polyalkoxyl group. In addition, in the present invention, a polyalkoxyl group refers to a group obtained by directly bonding two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. In the case where the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. As the above-mentioned alkyl group, an alkylene group, a divalent aromatic alkyl group or a group represented by a combination thereof is preferred, and an alkylene group is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 30 carbon atoms is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, and an alkylene group having 1 to 10 carbon atoms is further preferred. In the present invention, when simply described as "aliphatic alkyl group", "saturated aliphatic alkyl group", "alkyl group", "alkylene group", etc., unless otherwise specified, the groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl group" includes a straight chain alkyl group, a branched chain alkyl group, a cyclic alkyl group and an alkyl group represented by a combination thereof. As the aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, an aromatic alkyl group having 6 to 20 carbon atoms is more preferred, a phenylene group or a naphthylene group is further preferred, and a phenylene group is particularly preferred. As the alkylene group in the (poly)alkoxylene group, an alkylene group having 2 to 10 carbon atoms is preferred, an alkylene group having 2 to 4 carbon atoms is more preferred, an ethylene group or a propylene group is further preferred, and an ethylene group is further preferred. Furthermore, the number of alkoxylene groups contained in the polyalkoxylene group (the number of repetitions of the polyalkoxylene group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. In formula (P-3), Z ¹ represents an ether bond, an ester bond, a urethane bond, a urea bond or an amide bond, and an ester bond, a urethane bond, a urea bond or an amide bond is preferred. In formula (P-3), * represents a bonding site with Y ¹ .

Furthermore, from the viewpoint of drug resistance, the distance between the polymerizable group contained in ^A1 and the main chain of the specific resin is preferably 0 to 15, and more preferably 0 to 10. The distance between the polymerizable group contained in ^A1 and the main chain of the specific resin refers to the smallest number of atoms contained between the atoms contained in the main chain of the polyimide and the polymerizable group. For example, in the resin represented by formula (PI-1) in the examples described below, the distance between the methacryloyloxy group and the main chain is 4. That is, when the polyimide has a ring structure inside the main chain, "the atoms contained in the main chain of the above-mentioned polyimide" includes the ring members of the above-mentioned ring structure. Furthermore, when ^A1 contains a plurality of polymerizable groups, the distance between the polymerizable group closest to the main chain among the polymerizable groups contained in ^A1 and the main chain of the polyimide is preferably 0 to 15, and more preferably 0 to 10. Furthermore, when ^A1 contains a plurality of polymerizable groups, the distance between all the polymerizable groups contained in ^A1 and the main chain of the polyimide is further preferably 0 to 15, and particularly preferably 0 to 10.

When ^A1 is a group comprising at least one selected from the group consisting of an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A1 is preferably a group represented by the following formula P-4. [Chemical Formula 11] In formula (P-4), L ⁴ represents a single bond or an m+1 valent linking group, A ⁴ represents an aliphatic alkyl group, a polyalkylene oxide group or a group represented by such a bond, m represents an integer greater than 1, and * represents a bonding site with Y ^1. In formula (P-4), L ⁴ is preferably a single bond or a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N - or a group obtained by bonding two or more of such groups, more preferably an ester bond, an amide bond, a urea bond or a urethane bond, and even more preferably an ester bond. In formula (P-4), as the aliphatic alkyl group in A ⁴ , an alkyl group is preferred, a linear alkyl group or a branched alkyl group is more preferred, and a branched alkyl group is further preferred. The carbon number of the aliphatic alkyl group is preferably 4 to 30, and more preferably 6 to 20. In formula (P-4), as the group containing the polyalkylene oxide group in A ⁴ , the same groups as the group containing the polyalkylene oxide group in R ²² described later can be cited, and the preferred embodiment is also the same. In formula (P-4), A ⁴ may have the above-mentioned group containing a polymerizable group or other known substituents as substituents. In formula (P-4), m represents an integer greater than 1, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.

In formula (L-1), n1 represents an integer greater than or equal to 1, preferably an integer from 1 to 20, more preferably an integer from 1 to 10, further preferably an integer from 1 to 4, particularly preferably 1 or 2, and most preferably 1. When n1 is an integer greater than or equal to 2, the n1 ^A1s may be the same or different.

＜＜＜R ¹ and R ² ＞＞＞ In formula (R-1), R ¹ and R ² each independently represent a hydrogen atom or a alkyl group, preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and still more preferably a hydrogen atom.

-L ¹¹ - In formula (1-1), L ¹¹ represents a divalent linking group containing a polymerizable group. The polymerizable group in L ¹¹ preferably includes a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group, more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, and even more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. The number of polymerizable groups contained in ^L11 is preferably one or more, more preferably 1 to 15, further preferably 1 to 10, further preferably 1 to 5, one or two are particularly preferred, and one is most preferred. In terms of developing properties, ^L11 is preferably a group containing an aromatic hydrocarbon group, more preferably a group containing an aromatic hydrocarbon group having 6 to 30 carbon atoms, further preferably a group containing a benzene ring structure or a naphthalene ring structure, and particularly preferably a group containing a benzene ring structure.

＜＜Formula (L-2)＞＞ Wherein, ^L11 is preferably a group represented by the following formula (L-2). [Chemical Formula 12] In formula (L-2), ^Q1 represents an organic group having 1 to 30 carbon atoms, ^A2 represents a group containing a polymerizable group, n2 represents an integer greater than 1, and * represents a bonding site with other structures.

＜＜Q ¹ ＞＞ Q ¹ is preferably an n2+2 valent group containing an aromatic hydrocarbon group. The aromatic hydrocarbon group in Q ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a group obtained by removing two or more hydrogen atoms from a benzene ring, and particularly preferably a group obtained by removing three or more hydrogen atoms from a benzene ring. In formula (L-2), it is preferred that the bonding sites of Q ¹ to the two * described in formula (L-2) are both aromatic hydrocarbon groups. That is, it is preferred that the two nitrogen atoms described in formula (1-1) are directly bonded to the aromatic hydrocarbon ring structure contained in Q ¹ . In formula (L-2), it is preferred that the bonding sites of ^Q1 and ^A2 are both aromatic hydrocarbon groups. In other words, it is preferred that ^A2 is directly bonded to the aromatic hydrocarbon ring structure contained in ^Q1 .

^Q1 preferably comprises at least one structure selected from the group consisting of structures represented by the following formula (A2-1) to (A2-5), and more preferably at least one structure selected from the group consisting of structures represented by the following formula (A2-1) to (A2-5). [Chemical Formula 13] In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group or a halogenated alkylene group, and at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R A224 , R ^A231 to R A238 , R ^A241 to R A248 and R A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated ^alkyl group or a halogenated alkylene group. At least one of ^{R A238} , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 may be a bonding site with ^A2 in the above formula (L-2), and * each independently represents a bonding site with other structures.

Among them, from the viewpoint of solvent solubility, ^Q1 preferably includes a structure represented by any one of Formula (A2-1) to Formula (A2-4), and more preferably includes a structure represented by Formula (A2-1).

In formula (A2-1), R ^A211 to R ^A214 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. Preferably, from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is selected. A hydrogen atom or an alkyl group having 1 to 6 carbon atoms is further preferred. Examples of the halogenated alkyl group or the halogen atom in R ^A211 to R ^A214 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Preferably, the chlorine atom or the bromine atom is selected. Furthermore, at least one of ^RA211 to ^RA214 is preferably a bonding site with ^A2 in formula (L-2), and ^RA213 is more preferably a bonding site with ^A2 .

In formula (A2-2), R ^A221 to R ^A224 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), and preferred embodiments thereof are also the same. In addition, it is preferred that at least one of the above R ^A211 to R ^A214 is a bonding site with A ² in formula (L-2), and it is more preferred that one or two are bonding sites with A ² .

In formula (A2-3), R ^A231 to R ^A238 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments are also the same. In formula (A2-3), L ^A231 preferably represents a single bond, a divalent saturated alkyl group having 1 to 6 carbon atoms, a divalent unsaturated alkyl group having 5 to 24 carbon atoms, -O-, -S-, -NR ^N -, a ureido group, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, more preferably represents a single bond, a saturated alkyl group having 1 to 6 carbon atoms, -O-, or a heterocyclic group, and even more preferably represents a single bond or -O-. The above-mentioned ^RN is as described above, and preferred embodiments are also the same. Furthermore, at least one of the above-mentioned R ^A231 to R ^A238 is preferably a bonding site with A ² in formula (L-2), one or two are more preferably a bonding site with the above-mentioned A ² , and one of R ^A231 to R ^A234 and one of R ^A235 to R ^A238 are further preferably a bonding site with the above-mentioned A ² .

In formula (A2-4), R ^A241 to R ^A248 and L ^A241 have the same meanings as R ^A231 to R ^A238 and L ^A231 in formula (A2-3), respectively, and preferred embodiments thereof are also the same. In addition, it is preferred that at least one of the above R ^A241 to R ^A248 is a bonding site with A ² in formula (L-2), and it is more preferred that one or two are a bonding site with A ² , and it is further preferred that one of R ^A241 to R ^A244 and one of R ^A245 to R ^A248 are a bonding site with A ² .

In formula (A2-4), R ^A251 to R ^A258 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), and preferred embodiments thereof are also the same. In addition, it is preferred that at least one of the above R ^A251 to R ^A258 is a bonding site with A ² in formula (L-2), and it is more preferred that one or two are bonding sites with A ² , and it is further preferred that one of R ^A251 to R ^A254 and one of R ^A255 to R ^A258 are bonding sites with A ² .

＜＜A ² ＞＞ In formula (L-2), A ² represents a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group or a hydroxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred. The number of polymerizable groups contained in ^A2 is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one.

Furthermore, ^A2 is preferably a group represented by the above formula (P-1), and more preferably a group represented by the above formula (P-2) or the above formula (P-3).

＜＜n2＞＞ In formula (L-2), n2 represents an integer greater than or equal to 1, preferably an integer from 1 to 20, more preferably an integer from 1 to 10, further preferably an integer from 1 to 4, particularly preferably 1 or 2, and most preferably 1. When n2 is an integer greater than or equal to 2, the n2 ^A2s may be the same or different.

-Formula (2-1)- When the specific resin has a repeating unit represented by formula (1-1), it is preferred that the specific resin has a repeating unit represented by the following formula (2-1) as the repeating unit represented by formula (1-1). [Chemical Formula 14] In formula (2-1), ^X1 and ^X2 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^Y1 represents an organic group having 1 to 30 carbon atoms, ^Q1 represents an organic group having 1 to 30 carbon atoms, ^A1 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A2 represents a group containing a polymerizable group, ^R1 and ^R2 each independently represent a hydrogen atom or a monovalent organic group, and n1 and n2 each independently represent an integer greater than 1.

In the above formula (2-1), X ¹ , X ² , R ¹ and R ² have the same meanings as X ¹ , X ² , R ¹ and R ² in the above formula (R-1), and preferred embodiments thereof are also the same. In the above formula (2-1), Y ¹ , A ¹ and n1 have the same meanings as Y ¹ , A ¹ and n1 in the above formula (L-1), and preferred embodiments thereof are also the same. In the above formula (2-1), Q ¹ , A ² and n ² have the same meanings as Q ¹ , A ² and n ² in the above formula (L-2), and preferred embodiments thereof are also the same.

[Repeating unit represented by formula (1-2)] -R ²¹ - In formula (1-2), R ²¹ has the same meaning as R ¹¹ in formula (1-1), and preferred embodiments thereof are also the same.

-L ²¹ - In formula (1-2), L ²¹ has the same meaning as L ¹¹ in formula (1-1), and preferred embodiments are also the same.

-R ²² , R ²³ - R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group, and preferably are all monovalent organic groups. As the monovalent organic group in R ²² and R ²³ , there can be mentioned a group containing a polymerizable group or an organic group that may contain a heteroatom, and from the viewpoint of chemical resistance, developing properties, and solubility in solvents of specific resins, a group containing a polyalkylene oxide group is preferred.

＜＜Group containing a polymerizable group＞＞ The polymerizable group contained in the group containing a polymerizable group in R ²² and R ²³ includes preferably a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group, more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediimide group, a vinylphenyl group, an epoxy group, an oxycyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. The number of polymerizable groups contained in the above-mentioned group containing a polymerizable group is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one.

As the group containing a polymerizable group, a vinyl group, an allyl group, a (meth)acryl group or a group represented by the following formula (III) is also preferred.

[Chemical formula 15]

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

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a (poly) alkoxylene 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; and the number of repetitions is 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly) alkoxylene group represents an alkoxylene group or a polyalkoxylene group. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH ₂ CH (OH) CH ₂ -. More preferred are ethylene, propylene, trimethylene, and -CH ₂ CH (OH) CH ₂ -. Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group. In formula (III), * represents a bonding site with other structures.

<<Organic group that can contain heteroatoms>> The organic group that can contain heteroatoms is preferably an organic group that does not have a polymerizable group. As the heteroatom in the organic group that can contain the above-mentioned heteroatom, oxygen atom, nitrogen atom, sulfur atom, halogen atom, etc. can be cited, and oxygen atom is preferred. Moreover, the above-mentioned heteroatom is preferably contained as an ether bond (-O-). As the organic group that can contain the above-mentioned heteroatom, an organic group having 1 to 30 carbon atoms that can contain heteroatoms is preferred, and an organic group having 2 to 20 carbon atoms that can contain heteroatoms is preferred.

＜＜＜Polyalkylene oxide＞＞＞ Among them, the organic group that can contain the above-mentioned heteroatom is preferably an organic group containing polyalkylene oxide.

In the present invention, a polyalkoxyl group refers to a group obtained by directly bonding two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. In the case where the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. In addition, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, 2 to 10 is more preferred, 2 to 5 is further preferred, 2 to 4 is particularly preferred, and 2 is the best. As the polyalkoxy group, from the perspective of both solvent solubility and drug resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group obtained by bonding a plurality of polyethyleneoxy groups to a plurality of propoxy groups is preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the above-mentioned groups obtained by bonding multiple vinyloxy groups and multiple propoxy groups, the vinyloxy groups and propoxy groups can be arranged randomly, can be arranged in blocks, or can be arranged in alternating patterns. The preferred aspects of the number of repetitions of vinyloxy groups in these groups are as described above.

The organic group containing a polyalkylene oxide group is preferably a group represented by the following formula (PO-1). [Chemical Formula 16] In formula (PO-1), R ^P1 each independently represents an alkylene group, R ^P2 represents a monovalent organic group, n represents an integer greater than 2, L ^P1 represents a single bond or a divalent linking group, and * represents a bonding site to the oxygen atom to which R ²² or R ²³ in formula (1-2) is bonded.

In formula (PO-1), R ^{and P1} each independently represent preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group ( _-CH2 - _CH2- ) or a propylene group ( _-CH2 -CH( _CH3 )- or -CH( _CH3 ) _-CH2- ), and even more preferably an ethylene group.

In the formula (PO-1), R ^P2 represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group or a group containing a polymerizable group, and more preferably an alkyl group. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 2 to 4 carbon atoms is more preferred, and an ethyl group is further preferred. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. As the above-mentioned aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferred, an aralkyl group having 7 to 20 carbon atoms is more preferred, and a benzyl group is further preferred. The polymerizable group contained in the above-mentioned group containing a polymerizable group preferably includes a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group, and more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, and further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. As the above-mentioned group containing a polymerizable group, the group represented by the above-mentioned formula (P-1) is preferred, and the group represented by the above-mentioned formula (P-2) or the above-mentioned formula (P-3) is more preferred.

In the formula (PO-1), n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.

In formula (PO-1), L ^P1 represents a single bond or a divalent linking group, and a single bond is preferred. As the divalent linking group, a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N -, or a group obtained by bonding two or more of these groups is preferred, a alkyl group, -O-, -C(=O)-, -NR ^N -, or a group obtained by bonding two or more of these groups is more preferred, and a alkyl group, an ester bond, an amide bond, a urethane bond, a urea bond, or a group obtained by combining two or more of these groups is further preferred. The above-mentioned ^RN represents a hydrogen atom or a alkyl group, and a hydrogen atom, an alkyl group or an aryl group is more preferred, a hydrogen atom or an alkyl group is further preferred, and a hydrogen atom is particularly preferred. As the alkyl group in the above-mentioned L ^P1 , a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by such a bond is more preferred.

＜＜＜Halogen atom-substituted alkyl group＞＞＞ In addition, from the viewpoint of solvent solubility and film strength, the organic group that may contain a heteroatom may be a halogen atom-substituted alkyl group. As the halogen atom in the halogen atom-substituted alkyl group, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. As the above-mentioned alkyl group, an alkyl group or an aromatic alkyl group is preferred, and an alkyl group is more preferred. As the above-mentioned alkyl group, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 2 to 4 carbon atoms is further preferred. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, an aromatic alkyl group having 6 to 20 carbon atoms is more preferred, and a phenyl group is more preferred. That is, the halogen atom-substituted alkyl group is preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. By including a halogen atom-substituted alkyl group as R ²² or R ²³ , the film strength of the obtained cured film is improved.

＜＜Other substituents＞＞ R ²² and R ²³ may be other substituents. Examples of other substituents include alkyl groups having an acid group. Examples of alkyl groups having an acid group include alkyl groups having an acid group, aromatic alkyl groups having an acid group, and aralkyl groups having an acid group. As the alkyl group in the above-mentioned alkyl groups having an acid group, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, and an alkyl group having 1 to 10 carbon atoms is further preferred. As the acid group in the above-mentioned alkyl groups having an acid group, examples include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups, and carboxyl groups are preferred. As the aromatic hydrocarbon group in the above-mentioned aromatic hydrocarbon groups having an acid group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. As the above-mentioned aralkyl group having an acid group, an aralkyl group having 7 to 30 carbon atoms is preferred, an aralkyl group having 7 to 20 carbon atoms is more preferred, and a benzyl group is further preferred. As the above-mentioned aromatic hydrocarbon group having an acid group or the acid group in the above-mentioned aralkyl group having an acid group, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, etc. can be cited, and a phenolic hydroxyl group or a carboxyl group is preferred, and a phenolic hydroxyl group is more preferred. Among them, an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferred, an aromatic hydrocarbon group having a phenolic hydroxyl group or an aralkyl group having a phenolic hydroxyl group is more preferred, and a phenyl group having a phenolic hydroxyl group or a benzyl group having a phenolic hydroxyl group is further preferred. In addition, as other substituents, groups such as an alkyl group, an aryl group, an alkoxyalkyl group, and an aryloxyalkyl group can be mentioned.

From the viewpoint of film strength and chemical resistance, the molar amount of ^R22 and ^R23 as substituents containing ethylenic unsaturated bonds relative to the total molar amount of ^R22 and ^R23 in all repeating units represented by formula (1-2) contained in the specific resin is preferably 0 to 60%, and more preferably 0 to 30%. From the viewpoint of film strength, the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%. From the viewpoint of chemical resistance, the above ratio is preferably 10 to 30%, and more preferably 15 to 30%.

From the viewpoint of film strength, chemical resistance and solvent solubility of a specific resin, the molar amount of ^R22 and ^R23 , which are organic groups having 1 to 30 carbon atoms and which may contain a heteroatom, relative to the total molar amount of ^R22 and ^R23 in all repeating units represented by the above formula (1-2) contained in the above resin is preferably 20 to 100%. From the viewpoint of film strength, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more. From the perspective of drug resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, particularly preferably 80% or less, and best 70% or less.

From the viewpoint of film strength, chemical resistance and solvent solubility of a specific resin, the molar amount of the above R ²² and R ²³ as an organic group containing a polyalkoxy group relative to the total molar amount of R ²² and R ²³ in all the repeating units represented by the above formula (1-2) contained in the above resin is preferably 20 to 100%. The organic group containing a polyalkoxy group in the above ratio may be an organic group further containing a polymerizable group as long as it is an organic group containing a polyalkoxy group, but an organic group containing a polyalkoxy group and having no polymerizable group is preferred. From the viewpoint of film strength, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more. From the viewpoint of drug resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, particularly preferably 80% or less, and most preferably 70% or less. In addition, from the viewpoint of solubility in developer, for example, R ²¹ in the above formula (1-2) is set to a group containing at least one group selected from the group including the above aliphatic hydrocarbon group and polyalkylene oxide group as a substituent, and R ²² and R ²³ are also preferably set to the above other substituents. In this case, the ratio of the molar amount of the above R ²² and R ²³ as the above other substituents to the total molar amount of R ²² and R ²³ in the repeating unit represented by the above formula (1-2) is also preferably 50 to 100%.

-Formula (2-2)- When the specific resin has a repeating unit represented by formula (1-2), it is preferred that the specific resin has a repeating unit represented by the following formula (2-2) as the repeating unit represented by formula (1-2). [Chemical Formula 17] In formula (2-2), ^X3 and ^X4 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^Y2 represents an organic group having 1 to 30 carbon atoms, ^Q2 represents an organic group having 1 to 30 carbon atoms, ^A3 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A4 represents a group containing a polymerizable group, ^R3 and ^R4 each independently represent a hydrogen atom or a monovalent organic group, ^G1 and ^G2 each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer greater than 1.

In formula (2-2), ^X3 and ^X4 have the same meanings as ^X1 and ^X2 in formula (2-1), and a preferred embodiment thereof is also the same. In formula (2-2), ^R3 and ^R4 have the same meanings as ^R1 and ^R2 in formula (2-1), and a preferred embodiment thereof is also the same. In formula (2-2), ^Y2 , ^A3 and n3 have the same meanings as ^Y1 , ^A1 and n1 in formula (2-1), and a preferred embodiment thereof is also the same. In formula (2-2), ^Q2 , ^A4 and n4 have the same meanings as ^Q1 , ^A2 and n2 in formula (2-1), and a preferred embodiment thereof is also the same. In formula (2-2), ^G1 and ^G2 have the same meanings as ^R23 and ^R22 in the above formula (1-2), and preferred embodiments thereof are also the same.

Among them, it is preferred that the specific resin has a repeating unit represented by the above formula (2-1) as a repeating unit represented by the above formula (1-1) or has a repeating unit represented by the above formula (2-2) as a repeating unit represented by the above formula (1-2).

From the viewpoint of solvent solubility and developing properties, it is preferred that ^X1 and ^X2 in the above formula (2-1) are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms, and ^X3 and ^X4 in the above formula (2-2) are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms.

From the viewpoint of solvent solubility and developing properties, it is preferred that ^Y1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Y2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group.

From the viewpoint of solvent solubility and developing properties, it is preferred that ^Q1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Q2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group.

-Content of repeating units- The total content of the repeating units represented by formula (1-1) and the repeating units represented by formula (1-2) in the specific resin is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more relative to the total repeating units of the specific resin. The upper limit of the above content is not particularly limited as long as it is 100 mol% or less. In addition, the total content of the repeating units represented by formula (1-1) and the repeating units represented by formula (1-2) in the specific resin is preferably 50 mass% or more, more preferably 60 mass% or more, further preferably 70 mass% or more, and particularly preferably 80 mass% or more relative to the mass of the specific resin. There is no particular upper limit to the above content, as long as it is 100% by mass or less.

When the specific resin has a repeating unit represented by formula (1-1), the content of the repeating unit represented by formula (1-1) can be set to be 50 mol% or more relative to the total repeating units of the specific resin. The above content is more preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the above content is not particularly limited as long as it is 100 mol% or less. When the specific resin has a repeating unit represented by formula (1-2), the content of the repeating unit represented by formula (1-2) can be set to be 50 mol% or more relative to the total repeating units of the specific resin. The above content is preferably 60 mol% or more, 70 mol% or more is further preferred, and 80 mol% or more is particularly preferred. There is no particular upper limit to the above content, as long as it is 100 mol% or less.

When the specific resin has a repeating unit represented by formula (1-1), it may contain only one repeating unit represented by formula (1-1) or two or more repeating units represented by formula (1-1) of different structures. When the specific resin contains two or more repeating units represented by formula (1-1) of different structures, it is preferred that the total content of all repeating units represented by formula (1-1) contained in the specific resin is within the above content range. When the specific resin has a repeating unit represented by formula (1-2), it may contain only one repeating unit represented by formula (1-2) or two or more repeating units represented by formula (1-2) of different structures. In the case where the specific resin contains two or more repeating units represented by formula (1-2) of different structures, it is preferred that the total content of all repeating units represented by formula (1-2) contained in the specific resin is within the above content range.

Furthermore, when the specific resin has a repeating unit represented by formula (1-1), it is also preferred that the imidization rate (ring closure rate) of the specific resin is set to 70% or more. The above-mentioned imidization rate is more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the above-mentioned imidization rate, as long as it is 100% or less. The above-mentioned imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the specific resin is measured, and the peak intensity P1 near 1377 cm ^-1 , which is an absorption peak derived from the imide structure, is obtained. Next, the polyimide was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured again to determine the peak intensity P2 near 1377 cm ^-1 . The obtained peak intensities P1 and P2 can be used to determine the imidization rate of the specific resin according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

[Other repeating units] - Repeating units represented by formula (1) - The specific resin may also contain other repeating units. As other repeating units, the repeating units represented by the following formula (1) can be cited. The repeating units corresponding to the repeating units represented by the above formula (1-2) are set to be those that do not correspond to the repeating units represented by the following formula (1). In the case where the specific resin has the repeating units represented by the following formula (1), it is preferred that the specific resin contains the repeating units represented by the following formula (1) in the main chain. [Chemical Formula 18] In formula (1), A ^A1 and A ^A2 each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The repeating unit represented by the above formula (1) is a repeating unit in which the number of amide bonds contained in R ¹¹⁵ is one or less or R ¹¹¹ does not have a polymerizable group.

In formula (1), A ^A1 and A ^A2 each independently represent an oxygen atom or -NH-, preferably an oxygen atom. In formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, preferably a monovalent organic group. In addition, it is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both contain a polymerizable group. In addition, as the monovalent organic group in R ¹¹³ and R ¹¹⁴ , it is also preferred to cite the group containing a polymerizable group in R ²² and R ²³ in the above formula (1-2), which may contain an organic group of a heteroatom or other substituent.

In formula (1), R ¹¹⁵ may be the same structure as R ²¹ in formula (1-2). When R ¹¹⁵ in formula (1) is the same structure as R ²¹ in formula (1-2), R ¹¹¹ in formula (1) is a structure that does not contain a polymerizable group. In addition, R ¹¹⁵ is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). [Chemical Formula 19]

In formula (5), R ¹¹² is preferably a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, a group selected from -O-, -CO-, -S-, -SO ₂ - and NHCO-, and a combination thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, a group selected from -O-, -CO-, -S- and SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and SO ₂ -. In formula (5) and formula (6), * indicates a bonding site with other structures, respectively.

As for R ¹¹⁵ , specifically, there can be mentioned the tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic acid dianhydride. Only one type of tetracarboxylic acid dianhydride may be used, or two or more types may be used. The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). [Chemical Formula 20] In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as R ¹¹⁵ in formula (1), and the preferred range is also the same.

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

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

In formula (1), R ¹¹¹ may be the same structure as L ²¹ in formula (1-2). When R ¹¹¹ in formula (1) is the same structure as L ²¹ in formula (1-2), the number of amide bonds contained in R ¹¹⁵ in formula (1) is one or less. In formula (1), R ¹¹¹ may be a structure not containing a polymerizable group. Preferably, R ¹¹¹ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by bonding at least one of these groups with at least one of -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NR ^N - and a urea group. ^RN is as described above. As the aliphatic alkyl group, an aliphatic saturated alkyl group having 2 to 30 carbon atoms is preferred, and an aliphatic saturated alkyl group having 2 to 10 carbon atoms is more preferred. Furthermore, as the aliphatic alkyl group, a saturated aliphatic alkyl ring group having 6 to 20 ring members is preferred. As the aromatic alkyl group, an aromatic alkyl group having 6 to 20 carbon atoms is preferred, an aliphatic alkyl group having 6 to 12 carbon atoms is preferred, and an aromatic alkyl group having 6 carbon atoms is more preferred. Among them, from the viewpoint of solvent solubility, R ¹¹¹ is preferably a group containing an aliphatic alkyl ring group or an aromatic alkyl ring group, and is more preferably a group containing an aromatic alkyl ring group.

In view 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} has the same meaning as L ^A231 in the above formula (A2-3), and the preferred embodiment is also the same.

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 21]

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

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 22]

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

In formula (1), R ¹¹¹ is preferably a diamine. Examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, or 1,6-diaminohexane. ,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophorol Ketodiamine; 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'-diaminobiphenyl (4,4'-diaminodiphenylsulfone) Amino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(4-amino-3-carboxyphenyl)methane, 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'-diaminobiphenyl Triphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Diphenylmethane, 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, 4,6-dihydroxy-1,3-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, diaminobenzoic acid, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(2-aminophenyl)ethane (4-aminophenyl) hexafluoropropane, 1,4-bis(4-aminophenyl) octafluorobutane, 1,5-bis(4-aminophenyl) decafluoropentane, 1,7-bis(4-aminophenyl) tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4- At least one diamine selected from the group consisting of 2,4'-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'-hexafluorotolidine and 4,4'-diaminoquaternaryl.

Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred. Diamines having two or more alkylene glycol units described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 on the main chain can also be preferably used.

Examples of the diamine that imparts the structure of the above 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 may be used alone, or two or more may be used in combination.

In addition, the following diamine can also be preferably used. [Chemical Formula 23]

In order to improve the adhesion to the substrate, a diamine having a siloxane structure such as bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane can be used as the diamine component.

-Repeating units represented by formula (4)- The specific resin may also contain repeating units represented by formula (4). When the specific resin has repeating units represented by the following formula (4), it is preferred that the specific resin contains repeating units represented by the following formula (4) on the main chain. The repeating units represented by the above formula (1-1) are set to be those that do not correspond to the repeating units represented by formula (4). [Chemical Formula 24] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. In formula (4), R ¹³¹ and R ¹³² have the same meanings as R ¹¹¹ and R ¹¹⁵ in formula (1), respectively, and the preferred embodiments are also the same.

<<Content>> The total content of other repeating units in the specific resin is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less relative to the total mass of the specific resin. The lower limit of the above-mentioned total content is not particularly limited, as long as it is 0% by mass or more. In addition, from the perspective of the chemical resistance of the obtained cured film, as an aspect of the specific resin, it is also preferred that the other repeating units are substantially not contained. In this case, the total content of other repeating units is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less relative to the total mass of the specific resin. The lower limit of the above-mentioned total content is not particularly limited, as long as it is 0% by mass or more. The specific resin may contain only one other repeating unit, or may contain two or more other repeating units of different structures. In the case where the specific resin contains two or more other repeating units of different structures, it is preferred that the total content of all other repeating units contained in the specific resin is within the above content range.

-Terminal structure- The terminal structure of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, it can be sealed with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. Among these capping agents, monoamine is preferably used. As the monoamine, there can be mentioned aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Two or more of these can be used, and multiple different terminal groups can be introduced by reacting multiple end-capping agents.

[Content] From the viewpoint of improving the elongation at break of the obtained cured film, the content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more relative to the total solid content of the curable resin composition. As the upper limit of the above content, from the viewpoint of improving the resolution of the curable resin composition, 99.5% by mass or less is preferably, 99% by mass or less is more preferably, 98% by mass or less is even more preferably, 97% by mass or less is even more preferably, and 95% by mass or less is even more preferably.

[Physical properties of specific resin] -Molecular weight- The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and more preferably 10,000 to 100,000. The number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, and more preferably 4,000 to 50,000. Regarding the molecular weight dispersion of the specific resin, 1.5 to 3.5 is preferred, and 2 to 3 is more preferred. In this specification, the molecular weight dispersion means the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

-Acid value- The acid value of the specific resin is preferably 0 to 2.0 mmol/g, more preferably 0 to 1.5 mmol/g, and further preferably 0 to 1.0 mmol/g. When the curable resin composition is used for alkaline development described later, the acid value of the specific resin is preferably 1.2 to 7 mmol/g, more preferably 1.5 to 6 mmol/g, and further preferably 2 to 5 mmol/g. In the present invention, the acid value refers to the amount (mmol) of acid groups contained in 1 g of the specific resin. The acid group refers to a group neutralized by an alkali (e.g., sodium hydroxide) at a pH of 12 or higher. In addition, the above-mentioned acid group is preferably a group having a pKa of 10 or less. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. As the acid group, phenolic hydroxyl group, carboxyl group, sulfonic acid group, etc. can be cited, and carboxyl group is preferred.

[Polymerization group value] The molar amount of the polymerizable group contained in 1g of the specific resin (polymerization group value, unit: mmol/g) is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. When the specific resin contains ethylenic unsaturated bonds as polymerizable groups, the molar amount of ethylenic unsaturated bonds contained in 1g of the specific resin is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. When the specific resin contains polymerizable groups such as cyclic ether groups, hydroxymethyl groups, and alkoxymethyl groups as polymerizable groups, the molar amount of the above polymerizable groups contained in 1g of the specific resin is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g.

[Specific example] As a specific example of a specific resin, the specific resin used in the embodiment described below can be cited.

[Production method (production method of a specific resin having a repeating unit represented by formula (1-2))] When the specific resin has a repeating unit represented by formula (1-2), the specific resin is synthesized, for example, by a synthesis method shown in the synthesis example in the embodiment described later. In addition, the production method of the specific resin having a repeating unit represented by formula (1-2) preferably includes a step of reacting a diamine with a tetravalent carboxylic acid compound or a derivative thereof (precursor production step).

-Precursor production step- As the diamine used in the above-mentioned precursor production step, there can be mentioned the diamine represented by the following formula (DA-1). [Chemical formula 25] In formula (DA-1), L ²¹ has the same meaning as L ²¹ in formula (1-2), and the preferred embodiment is also the same. In addition, by further using the diamine described in the description of formula (1), the repeating unit represented by formula (1) can also be introduced into a specific resin. The tetravalent carboxylic acid oxide compound used in the above-mentioned precursor production step can be a carboxylic acid dianhydride, or a compound in which two of the four carboxyl groups are modified by esterification, halogenation, etc. Preferably, among the carboxylic acid dianhydrides represented by the following formula (DC-1), a compound in which two of the four carboxyl groups after hydrolysis are esterified can be cited. It is preferred that R ²² and R ²³ in the above-mentioned formula (1-2) are introduced by the above-mentioned esterification. Furthermore, it is preferred that the compound in which two of the four carboxyl groups are esterified is halogenated using a halogenating agent and then reacted with a diamine. In addition, the reaction conditions in the precursor production step can be appropriately determined by referring to known esterification conditions.

Furthermore, in the precursor production step, it is preferable to use an organic solvent when carrying out the reaction. The organic solvent may be one kind or two or more kinds. As the organic solvent, it can be appropriately set according to the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

In the precursor preparation step, it is preferred to include a solid precipitation step. Specifically, the specific resin in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby being able to precipitate a solid.

-Diamine production step- The method for producing a specific resin may include the following step (diamine production step), that is, reacting a compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group with a compound B having a group that can form a bond with the reactive group and a polymerizable group, and after obtaining a compound C in which the compound A and the compound B are bonded, the nitro group in the compound C is reduced to obtain a diamine. The diamine obtained in the diamine production step is used as the diamine in the precursor production step.

The reactive group in compound A is not particularly limited, and examples thereof include amino, hydroxyl, and carboxyl groups. Compound A preferably has a structure in which two nitro groups and at least one reactive group are directly bonded to an aromatic hydrocarbon group.

The group that can form a bond with the reactive group in compound B is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an epoxy group, and an isocyanate group. Examples of the polymerizable group in compound B include the groups exemplified as the group included in ^L22 in the above formula (1-2).

Compound C is a group obtained by the reaction of compound A and compound B, and is a compound having two nitro groups and a group containing at least one polymerizable group. The diamine compound is obtained by reducing the nitro group in compound C. As the reduction method, Bechamp reduction, hydrogenation reaction using a metal catalyst such as palladium, platinum, nickel and a hydrogen source such as hydrogen gas or ammonium formate, and reduction method using a metal hydride as a reducing agent can be used.

For example, the synthesis of the dinitro compound (A-1) in the following examples is a reaction in which 3,5-dinitrobenzoyl chloride as compound A is reacted with 2-hydroxyethyl methacrylate as compound B to obtain the dinitro compound (A-1) as compound C. Also, the synthesis of the diamine (AA-1) in the following examples is a reaction in which two nitro groups in the dinitro compound (A-1) as compound C are reduced to obtain the diamine (AA-1).

-Carboxylic acid dianhydride production step- The production method of the specific resin may include a step of reacting a diamine compound with a compound having one carboxylic acid anhydride group and one carboxyl group to obtain a carboxylic acid dianhydride having two or more amide bonds (carboxylic acid dianhydride production step). The one carboxyl group may be a carboxylic acid halide group. The details of the above reaction may be determined by referring to a known amidation method. For example, the synthesis of anhydride (MA-1) in the embodiment described below is a reaction of reacting AA-1 as a diamine compound with trimellitic anhydride chloride as a compound having one carboxylic acid anhydride group and one carboxylic acid halide group to obtain anhydride (MA-1) having two amide bonds. As the obtained carboxylic acid dianhydride, there can be mentioned the compound represented by the following formula (DC-1). [Chemical Formula 26] In formula (DC-1), R ²¹ has the same meaning as R ²¹ in formula (1-2), and the preferred embodiment is also the same.

[Production method (production method of a specific resin having a repeating unit represented by formula (1-2))] When the specific resin has a repeating unit represented by formula (1-2), the specific resin is synthesized, for example, by a synthesis method shown in a synthesis example in the embodiment described later. In addition, the production method of a specific resin having a repeating unit represented by formula (1-1) may include an imidization step of imidizing the specific resin having a repeating unit represented by the above formula (1-2).

In the imidization step, the specific resin having the repeating unit represented by formula (1-2) obtained in the above-mentioned precursor production step is imidized, thereby obtaining the specific resin having the repeating unit represented by formula (1-1). The imidization step may be any of thermal imidization (e.g., imidization based on heating), chemical imidization (e.g., imidization using a catalyst), and imidization based on a combination thereof, for example, by heating in the presence of a catalyst such as an amine compound. In addition, in the imidization step, for example, a dehydrating agent may be used. As the dehydrating agent, carboxylic anhydrides such as acetic anhydride and the like may be mentioned. In addition, the details of imidization can be carried out by a known method.

-Other production methods- In addition, the production method of a specific resin having a repeating unit represented by formula (1-1) may be a method in which a carboxylic acid dianhydride and a diamine compound are reacted and then heated at a high temperature and dehydrated to synthesize the resin in one stage. As the carboxylic acid dianhydride, for example, the carboxylic acid dianhydride represented by the above formula (DC-1) can be cited. The above carboxylic acid dianhydride is preferably a compound obtained in the above tetravalent carboxylic acid production step. As the diamine compound, the diamine compound represented by the above formula (DA-1) can be used. Further, the production method of the resin used in the present invention may be a method in which a carboxylic acid dianhydride and a diisocyanate compound are reacted and then decarboxylated at a high temperature to synthesize the resin in one stage. As the carboxylic acid dianhydride, for example, the carboxylic acid dianhydride represented by the above formula (DC-1) can be cited. The above carboxylic acid dianhydride is preferably a compound obtained in the above quaternary carboxylic acid production step. As the diisocyanate compound, a compound in which two amino groups in the compound represented by the above formula (DA-1) are respectively changed to isocyanate groups can be cited. For details of such production methods, reference can be made to the known synthesis method of polyimide.

Furthermore, the method for producing the resin used in the present invention may be a method comprising the steps of reacting a compound having three carboxyl groups or a derivative of the compound having three carboxyl groups with a first diamine compound or a diisocyanate compound to obtain a compound D having two imide ring structures and two carboxylic acids, and reacting the compound D with a second diamine compound to obtain a resin. As the compound having three carboxyl groups or the derivative of the compound having three carboxyl groups, there can be cited a compound having three carboxyl groups, a compound having one carboxyl group and one carboxylic acid anhydride group, a compound having one carboxylic acid halide group and one carboxylic acid anhydride group, a compound having one carboxylate group and one carboxylic acid anhydride group, a compound having three carboxylate groups, a compound having one carboxylate halide group and two carboxylate groups, and the like. As the first diamine compound, specifically, a diamine compound represented by the above formula (DA-1) can be used. As the diisocyanate compound, specifically, a compound in which two amine groups in the compound represented by the above formula (DA-1) are respectively changed to isocyanate groups can be cited. Regarding the above reaction conditions, etc., it is sufficient to refer to the known imidization reaction and appropriately determine them.

As the second diamine compound, there can be mentioned a diamine compound represented by the following formula (DA-2). [Chemical Formula 27] In formula (DA-2), L ³ has the same meaning as L ³ in formula (R-1), and the preferred embodiment is the same. The reaction conditions in the step of obtaining the above resin can be appropriately determined by referring to the known method for producing polyamide.

<Polymerization initiator> The curable resin composition of the present invention contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred.

[Photopolymerization initiator] The curable resin composition of the present invention preferably contains a photopolymerization initiator as a polymerization 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 in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active radicals by generating some effects with a photoexcited sensitizer.

The photo-free 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 using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) and 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 above details, 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, and the contents are incorporated into this specification.

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

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127, and IRGACURE 727 (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 (product names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matching 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 (product 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 a photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure tolerance can be more effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, 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 the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 28]

Among the commercial 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.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 29]

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and compounds described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 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 preferably 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.

Further preferred photoradical polymerization initiators are trihalogenomethyl trioxime 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. At least one compound selected from the group consisting of trihalogenomethyl trioxime compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds is further preferred. Using metallocene compounds or oxime compounds is further preferred, and oxime compounds are further preferred.

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

[Chemical formula 30]

In formula (I), R ^I00 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, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; R ^I01 is a group represented by formula (II) or a group identical to R ^I00 ; and R ^I02 to R ^I04 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 31]

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 also include the 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 % relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass %. The photopolymerization initiator may contain only one or more. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

<Thermal polymerization initiator> The curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain 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 polymerization reaction of the specific resin and the polymerizable compound can also be carried out in the heating step described later, thereby further improving the chemical 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 polymerization initiator is included, 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 polymerization initiator may be contained in one type or in two or more types. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

[Photoacid generator] In addition, the curable resin composition of the present invention may contain a photoacid generator as a polymerization initiator. The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinone diazonium compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as amide sulfonates, oxime sulfonates, diazo disulfonates, disulfonates, and o-nitrobenzyl sulfonates.

Examples of the quinone diazide compound include those obtained by bonding sulfonic acid ester of quinone diazide to a polyhydroxy compound, those obtained by bonding sulfonic acid sulfonamide of quinone diazide to a polyamine compound, and those obtained by bonding sulfonic acid of quinone diazide to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferred that 50 mol% or more of the functional groups of the polyhydroxy compound or polyamine compound are substituted with quinone diazide.

In the present invention, as the quinone diazide, at least one of 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl can be preferably used. 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of mercury lamp and is suitable for i-ray exposure. 5-naphthoquinone diazide sulfonyl compound has absorption extending to the g-ray region of mercury lamp and is suitable for g-ray exposure. In the present invention, 4-naphthoquinone diazide sulfonyl compound and 5-naphthoquinone diazide sulfonyl compound are preferably selected according to the exposure wavelength. Furthermore, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group may be contained in the same molecule, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may also be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonyl compound, or by a known method. By using such naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of such compounds, etc. can be cited.

As the onium salt compound or sulfonate salt compound, compounds described in paragraphs 0064 to 0122 of Japanese Patent Application No. 2008-013646 can be cited. In addition, as the photoacid generator, commercially available products can be used. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FFUJIFILM Wako Pure Chemical Corporation).

When a photoacid generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the curable resin composition of the present invention. The photoacid generator may contain only one type or two or more types. When two or more types of photoacid generators are contained, the total amount thereof is preferably within the above range.

<Thermal acid generator> The curable resin composition of the present invention may contain a thermal acid generator as a polymerization initiator. The thermal acid generator has the effect of generating acid by heating and promoting the crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound, or a hydroxymethyl group contained in a specific resin. In addition, when the curable resin composition of the present invention contains a thermal acid generator, it is preferred that the specific resin contains a hydroxymethyl group or an alkoxymethyl group as a polymerizable group.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a thermal acid generator is selected that does not generate acid when the curable resin composition is applied to the substrate and dried (pre-baking: about 70 to 140°C), but generates acid when finally heated (curing: about 100 to 400°C) after patterning in subsequent exposure and development, it is preferred because the sensitivity drop during development can be suppressed. The thermal decomposition start temperature is obtained as the peak temperature of the lowest temperature heat peak when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule. As equipment used to measure the thermal decomposition start temperature, Q2000 (manufactured by TA Instruments.) can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogen sulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the cured film and less reduction in the physical properties of the cured film, the one that generates an alkanesulfonic acid having 1 to 4 carbon atoms or a halogen alkanesulfonic acid having 1 to 4 carbon atoms is more preferred. As the thermal acid generator, (4-hydroxyphenyl) dimethyl konjac salt of methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethyl konjac salt of methanesulfonate, benzyl (4-hydroxyphenyl) methyl konjac salt of methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl) methyl konjac salt of methanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) konjac salt of methanesulfonate, (4-hydroxyphenyl) trifluoromethanesulfonate, trifluoromethanesulfonate benzyl(4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copper salt, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred.

Furthermore, as the thermal acid generator, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferred.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, from the viewpoint of the electrical insulation of the cured film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

<Polymerizable compound> The curable resin composition of the present invention preferably contains a polymerizable compound. In this specification, the compound corresponding to the above-mentioned specific resin is set as one that does not correspond to the polymerizable compound. As the polymerizable compound, a polyfunctional polymerizable compound is preferred. In this specification, a polyfunctional polymerizable compound refers to a compound having two or more polymerizable groups. In addition, as the polymerizable compound, a free radical polymerizable compound is preferred, and a compound having two or more free radical polymerizable groups is more preferred.

[Free radical polymerizable compound] As the polymerizable compound, a free radical polymerizable compound can be used. The free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, there can be mentioned groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, and (meth)acryloyl. The free radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferred.

The number of radical polymerizable groups possessed by the radical polymerizable compound may be one or two or more. The radical polymerizable compound preferably has two or more radical polymerizable groups, and more preferably has 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 radical polymerizable compound having two or more functional groups, and more preferably contains at least one radical polymerizable compound having three or more functional groups. In addition, it may be a mixture of a radical polymerizable compound having two or more functional groups and a radical 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 radical 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 an affinity substituent such as a hydroxyl group, an amino group, or a thiohydride group 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, a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can also be used to replace the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, 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, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol 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)acrylating the obtained compound. Compounds obtained by esterification, such as (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 multifunctional acrylates or methacrylates, and mixtures thereof. In addition, 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 compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid may 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, or cardo resins described in Japanese Patent Application Laid-Open Nos. 2010-160418, 2010-129825, and 4364216, 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, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of 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 are incorporated into the present specification.

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

Furthermore, 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 groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

As commercially available products of the radical polymerizable compound, for example, 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.), 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. The free radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is more preferably a free radical polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. Particularly preferred is a compound in which the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol among free radical polymerizable compounds having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510 and M-520.

The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and the particularly preferred acid value is 5 to 30 mgKOH/g. As long as the acid value of the radical polymerizable compound is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerizability is good. In addition, from the perspective of the developing speed during alkaline development, the preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and the particularly preferred acid value is 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

In the curable resin composition of the present invention, from the viewpoint of suppressing warping accompanying control of the elastic modulus of the cured film, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. As the monofunctional free radical polymerizable compound, preferably used are (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, and polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. As a monofunctional free radical polymerizable compound, in order to suppress volatility before exposure, a compound having a boiling point of 100°C or more at normal pressure is also preferred. In addition, from the perspective of pattern resolution and film stretchability, it is also preferred to use a bifunctional methacrylate or acrylate. As a specific compound, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate can be used. Acid ester, dihydroxymethyl tricyclodecane diacrylate, dihydroxymethyl tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bonds, bifunctional methacrylate with urethane bonds. Two or more of these can be used in combination as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of about 200.

[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, the compound represented by the following formula (AM1), formula (AM4) or formula (AM5) is preferred.

[Chemical formula 32] (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 33] (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 34] (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 formula (AM4) include 46DMOC, 46DMOEP (product 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 (product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.

Specific examples of the compound represented by 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 are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (these are product names, manufactured by Sanwa Chemical Co., Ltd.).

-Epoxy compounds (compounds having epoxy groups)- As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C, and dehydration reaction caused by crosslinking does not occur, so it is not easy to cause film shrinkage. Therefore, containing epoxy compounds is effective in inhibiting low-temperature curing and warping of curable resin compositions.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus 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 group-containing polysiloxanes such as polymethyl (glycidoxypropyl) 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) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-485 0-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above are product names, DIC CORPORATION), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, ADEKA CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the perspective of suppressing warp and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

-Oxycyclobutane compounds (compounds having an oxycyclobutyl group)- Examples of oxycyclobutane compounds include 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, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-Benzotriazole compounds (compounds having polybenzotriazole groups)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzotriazole compound does not produce degassing during curing, thereby further reducing thermal shrinkage to suppress the occurrence of warping, so it is preferred.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (the above are product 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.

The content of the polymerizable compound is preferably more than 0 mass % and 60 mass % or less 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 polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount is preferably 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, sulfides, amides, ureas, and alcohols.

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

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, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, 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, 3-methylcyclohexanone, levoglucosanone, dihydroglucosanone and the like are preferably mentioned.

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

As the sulfoxides, for example, dimethyl sulfoxide can be preferably mentioned.

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferably mentioned.

As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

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

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

In the present invention, a solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 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 is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferred.

From the viewpoint of coating properties, the content of the solvent is preferably set to an amount of 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 %, further preferably 10 to 70 mass %, and further preferably 40 to 70 mass %. The content of the solvent can be adjusted according to the desired thickness of the coating film and the coating method.

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

<Other resins> The curable resin composition of the present invention may also contain other resins different from the above-mentioned specific resin (hereinafter, also referred to as "other resins" for short). As other resins, polyimide of a different type from the specific resin, polyimide precursor of a different type from the specific resin, polysiloxane, resin containing a siloxane structure, epoxy resin, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and a cured film with excellent chemical resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, an acrylic resin with a high polymerizable base value of 20,000 or less is added to the composition, thereby improving the coating properties of the composition, the chemical resistance of the cured film, etc.

[Polyimide (other resins)] From the viewpoint of the film strength of the obtained cured film, it is preferable that the polyimide as the other resin has a repeating unit represented by the above formula (4). In the polyimide, the repeating unit represented by the formula (4) may be one type or two or more types. In addition to the repeating unit of the above formula (4), the polyimide may also contain other types of repeating units.

As an embodiment of the polyimide of the present invention, a polyimide precursor can be exemplified in which 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 (4). The upper limit is practically 100 mol% or less.

The weight average molecular weight (Mw) of the polyimide 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 polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.

Polyimide can be obtained, for example, by cyclizing a polyimide precursor, which is another resin described later, by heating.

[Polyimide precursor (other resins)] From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably has a repeating unit represented by the above formula (1).

In the polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. Furthermore, the polyimide precursor may contain structural isomers of the repeating unit represented by formula (1). Furthermore, in addition to the repeating unit of formula (1), the polyimide precursor may 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 especially 90 mol% or more of the total repeating units are the 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, more preferably 2 to 3.

The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, the polyimide 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 set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

When preparing the polyimide precursor, it is preferred to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby precipitating a solid.

When the curable resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to the total solid content of the curable resin composition. In addition, the content of the other resins in the curable resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less relative to the total solid content of the curable resin composition. In addition, as a preferred embodiment of the curable resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the curable resin composition is preferably 20% by mass or less, 15% by mass or less is more preferably, 10% by mass or less is further preferably, 5% by mass or less is further preferably, and 1% by mass or less is further preferably. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The curable resin composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, the total amount is preferably within the above range.

<Onium salt> The curable resin composition of the present invention preferably contains an onium salt. In particular, when the curable resin composition contains a resin having a repeating unit represented by formula (1-2) as a specific resin, the curable resin composition preferably contains a thermal alkali generator. The type of onium salt is not particularly limited, and preferably includes ammonium salts, imide salts, cobalt salts, iodine salts, or phosphonium salts. Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodine salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

In addition, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded via covalent bonding or not. That is, an onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt in which a cation molecule and anion molecule that are separate molecules are ionically bonded, and an intermolecular salt is preferred. Furthermore, in the curable resin composition of the present invention, the cationic part or cationic molecule and the anionic part or anionic molecule can be bonded or dissociated by ionic bonding. As the cation in the onium salt, ammonium cation, pyridinium cation, coronium cation, iodine cation or phosphonium cation is preferred, and at least one cation selected from the group including tetraalkylammonium cation, coronium cation and iodine cation is more preferred.

The onium salt used in the present invention may be a thermal alkali generator. The thermal alkali generator refers to a compound that generates an alkali by heating, for example, an acidic compound that generates an alkali when heated to 40°C or above.

[Ammonium salt] In the present invention, ammonium salt refers to a salt of ammonium cations and anions.

-Ammonium cation- As the ammonium cation, a quaternary ammonium cation is preferred. Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 35] In formula (101), R ¹ to R ⁴ each independently represents a hydrogen atom or a hydrocarbon group, and at least two of R ¹ to R ⁴ may be bonded to form a ring.

In formula (101), R ¹ to R ⁴ are each independently preferably a alkyl group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. When at least two of R ¹ to R ⁴ are bonded to form a ring, the ring may contain a heteroatom. Examples of the heteroatom include a nitrogen atom.

The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2). [Chemical Formula 36]

In formula (Y1-1) and (Y1-2), R ¹⁰¹ represents an n-valent organic group, R ¹ has the same meaning as R ¹ in formula (101), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aromatic group, and n represents an integer greater than 1. In formula (Y1-1), R ¹⁰¹ is preferably a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and is more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

-Anions- As the anion in the ammonium salt, one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions is preferred, and carboxylate anions are more preferred from the viewpoint of being able to take both the stability and thermal decomposition of the salt into consideration. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylate anions. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. According to this aspect, the stability, curability and developing properties of the curable resin composition can be further improved. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developing properties of the curable resin composition can be further improved.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 37] In formula (X1), EWG represents an electron-withdrawing group.

In the present embodiment, the electron-withdrawing group indicates a group whose Hammett substituent constant σm is a positive value. σm is described in detail in Yufu Mitsuno's Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. Examples of substituents whose σm represents a positive value include CF ₃ group (σm=0.43), CF ₃ C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH ₂ =CH group (σm=0.06), Ac group (σm=0.38), MeOC (=O) group (σm=0.37), MeC (=O) CH=CH group (σm=0.21), PhC (=O) group (σm=0.34), H ₂ NC (=O) CH ₂ group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

Preferably, EWG is a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 38] In formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical Formula 39] In formula (XA), ^L10 represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, ^-NRX- , and combinations thereof, and ^RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion and an oxalate anion.

From the viewpoint that the specific resin is easy to be cyclized at low temperature and the storage stability of the curable resin composition is easy to be improved, the onium salt in the present invention contains ammonium cations as cations, and the onium salt contains anions with a pKa (pKaH) of 2.5 or less of the conjugated acid as anions, and it is more preferable to contain anions with a pKa (pKaH) of 1.8 or less. The lower limit of the above pKa is not particularly limited, and from the viewpoint that the generated base is not easy to neutralize and the cyclization efficiency of the specific resin is improved, -3 or more is preferred, and -2 or more is more preferred. As the above pKa, the values described in Determination of Organic Structures by Physical Methods (author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; editor: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values calculated from the structural formula using the software ACD/pKa (manufactured by ACD/Labs) were used.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 40]

[Imine salt] In the present invention, the imine salt refers to a salt of an imine cation and an anion. As the anion, the same anion as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred embodiment is also the same.

-Imine cation- As the imine cation, pyridinium cation is preferred. Also, as the imine cation, the cation represented by the following formula (102) is also preferred. [Chemical Formula 41]

In formula (102), ^R5 and ^R6 each independently represent a hydrogen atom or a alkyl group, ^R7 represents a alkyl group, and at least two of ^R5 to ^R7 may be bonded to form a ring. In formula (102), ^R5 and ^R6 have the same meanings as ^R1 to ^R4 in formula (101), and preferred embodiments are also the same. In formula (102), it is preferred that ^R7 is bonded to at least one of ^R5 and ^R6 to form a ring. The above ring may also contain a heteroatom. As the above heteroatom, a nitrogen atom may be cited. In addition, as the above ring, a pyridine ring is preferred.

The imide cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical Formula 42] In formula (Y1-3) to (Y1-5), ^R101 represents an n-valent organic group, ^R5 has the same meaning as ^R5 in formula (102), ^R7 has the same meaning as ^R7 in formula (102), n represents an integer greater than 1, and m represents an integer greater than 0. In formula (Y1-3), ^R101 is preferably a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 43]

[Sirconium salt] In the present invention, the "sirconium salt" refers to a salt of a cation and an anion of a iron. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiment is also the same.

- Copper cation - As the copper cation, a tertiary copper cation is preferred, and a triaryl copper cation is more preferred. In addition, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical formula 44]

In formula (103), R ⁸ to R ¹⁰ each independently represents a alkyl group. R ⁸ to R ¹⁰ each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferred that they are the same group.

[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiments are also the same.

-Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 45]

In formula (104), R ¹¹ and R ¹² each independently represent a alkyl group. R ¹¹ and R ¹² each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferred that they are the same group.

[Phosphonium salt] In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations. Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical Formula 46]

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a alkyl group. R ¹³ to R ¹⁶ each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthetic suitability, the same group is preferred.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is preferably 0.5 mass % or more, 0.85 mass % or more is further preferred, and 1 mass % or more is further preferred. The upper limit is preferably 30 mass % or less, 20 mass % or less is further preferred, and 10 mass % or less is further preferred. It can be 5 mass % or less, and can also be 4 mass % or less. Onium salts can be used one or more. When two or more are used, the total amount is preferably within the above range.

<Thermoalkali generator> The curable resin composition of the present invention may contain a thermoalkali generator. In particular, when the curable resin composition contains a resin having a repeating unit represented by formula (1-2) as a specific resin, it is preferred that the curable resin composition contains a thermoalkali generator. The thermoalkali generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermoalkali generator other than the above-mentioned onium salt. As another thermoalkali generator, a non-ionic thermoalkali generator may be mentioned. As a non-ionic thermoalkali generator, a compound represented by formula (B1) or formula (B2) may be mentioned. [Chemical Formula 47]

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

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

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

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or aralkyloxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aralkenyl, and aralkyloxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 48]

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 are the same as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within a range in which the effects of the present invention are exerted. Among them, ^Rb13 is preferably an aralkyl group.

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

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

Furthermore, the compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 49]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

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

Among the above-mentioned onium salts, the following compounds can be cited as specific examples of compounds serving as thermal alkali generators or other specific examples of thermal alkali generators. [Chemical Formula 50] [Chemical formula 51]

[Chemical formula 52]

The content of the alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Migration inhibitor> The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively inhibit the migration of metal ions from the metal layer (metal wiring) 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, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazole 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, 5-phenyltetrazole, 5-methylbenzotriazole, and 4-methylbenzotriazole 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 53]

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 % relative to the total solid content of the curable resin composition.

The migration inhibitor may be one or more than one. When there are two or more migration inhibitors, the total amount is preferably 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, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, 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, phenathiophene, N-nitrosodiphenylamine, N-phenylnaphthylamine, 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-nitrosophenylhydroxylamine first barium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 ,5-trioxa-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl radical, phenothiazine, 1,1-diphenyl-2-pyrrolohydrazide, dibutyl copper dithiocarbonate (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent 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 be used.

[Chemical formula 54]

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0 mass %, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % relative to the total solid content of the curable resin composition of the present invention.

The polymerization inhibitor may be one or more than one. When there are two or more polymerization inhibitors, the total amount is preferably 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 metal adhesion improvers include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure and compounds having thiourea, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

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 55]

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used. Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

Examples of the aluminum-based bonding agent include aluminum tri(ethyl acetylacetate), aluminum tri(acetylacetone), and aluminum diisopropyl acetylacetate.

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 specific resin. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing step 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 step 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 amount is within the above range.

<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, photobase generators, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When such additives are formulated, it is preferred that the total amount is set to 3% by weight or less of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may have 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 curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat, etc. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator cause a chemical change and decompose to generate free radicals, acids, or bases. As the sensitizer, sensitizers such as N-phenyldiethanolamine can be cited. In addition, a sensitizing pigment can also be used as a sensitizer. For details about the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Application No. 2016-027357, and the contents are incorporated into this manual.

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 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 have 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 compound group 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 can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

Furthermore, 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 of the curable resin composition of the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, the total amount is preferably within the above range.

[Surfactant] From the viewpoint 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, and silicone-based surfactants 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 chain represent the number of repetitions of each repeating unit. [Chemical Formula 56] Furthermore, the surfactant may also include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. The fluorine-based surfactant may also include compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503. Block polymers can also be used as fluorine-based surfactants. As specific examples, compounds described in Japanese Patent Publication No. 2011-089090 can be cited. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds, which contain repeating units from (meth)acrylate compounds having fluorine atoms and repeating units from (meth)acrylate compounds having two or more (preferably 5 or more) alkoxy groups (preferably ethyleneoxy and propyleneoxy groups). Fluorine-based surfactants can also use fluorine-containing polymers having ethylenically unsaturated groups on the side chains as fluorine-based surfactants. As specific examples, there are compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. In terms of uniformity of the thickness of the coating film or liquid saving, the fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

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

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

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Co., Ltd.) etc.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

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

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 amount is preferably within the above range.

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

Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

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% by 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 amount is preferably within the above range.

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

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The mechanical properties of the cured film may be deteriorated by containing a large amount of the average particle size of the inorganic particles. Furthermore, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of the exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorber can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of tris(iodine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris(iodine-based ultraviolet absorbers), 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium, etc.; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)trisinium compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-trisinium and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium; 2,4-bis(2-hydroxy-4- tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota).

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may contain ultraviolet absorbers or may not contain ultraviolet absorbers, but when contained, the content of ultraviolet absorbers is preferably 0.001 mass% or more and 1 mass% or less, and more preferably 0.01 mass% or more and 0.1 mass% or less relative to the total solid content of the composition of the present invention.

[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains the organic titanium compound, a resin layer with excellent chemical resistance can be formed even when hardening at a low temperature.

As the organic titanium compound that can be used, there can be cited those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, the storage stability of the negative photosensitive resin composition is excellent, and a good curing pattern can be obtained, so a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples include titanium diisopropyl alcohol bis(triethanolamine), titanium di(n-butyl alcohol) bis(2,4-pentanedione), titanium diisopropyl alcohol bis(2,4-pentanedione), titanium diisopropyl alcohol bis(tetramethylheptanedione), titanium diisopropyl alcohol bis(ethyl acetylacetate), etc. II) Tetraalkoxy titanium compounds: for example, titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethanol, titanium tetramethoxypropanol, titanium tetramethylphenoxide, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], etc. III) Titanium bis(cyclopentadienyl)trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxy compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium salt, etc.

Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, titanium diisopropylate bis(ethyl acetylacetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) are preferred.

When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds and thioether compounds can be cited. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position) are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-t-butyldibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-2-yl)oxy]ethyl]amine, and phosphite ethylbis(2,4-di-t-butyl-6-methylphenyl). As commercially available antioxidants, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80 and Adekastab AO-330 (all manufactured by ADEKA CORPORATION) can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention can contain a latent antioxidant as needed. As a latent antioxidant, there can be mentioned a compound in which a portion that functions as an antioxidant is protected by a protecting group, and the protecting group is removed by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst to function as an antioxidant. As a latent antioxidant, there can be mentioned compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219. As a commercially available product of a latent antioxidant, there can be mentioned ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. As examples of preferred antioxidants, there can be cited 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

[Chemical formula 57]

In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R6 represents an alkylene group having 2 or more carbon atoms, R7 represents a monovalent to tetravalent organic group including at least one of an alkylene group having 2 or more carbon atoms, an O atom, and a N atom, and k represents an integer of 1 to 4.

The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, it can inhibit metal oxidation by its rust-proofing effect on metal materials.

It can act on the resin and the metal material at the same time, so k is preferably an integer of 2 to 4. As R7, alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, combinations thereof, etc. can be cited, and it may have a substituent. Among them, alkyl ether and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion when forming a metal complex.

The compounds represented by the following general formula (3) can be exemplified as follows, but are not limited to the following structures.

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

The amount of antioxidant added is preferably 0.1 to 10 parts by weight relative to the resin, and more preferably 0.5 to 5 parts by weight. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the elongation characteristics and the adhesion to the metal material after the reliability is improved, and when the amount added is more than 10 parts by weight, there is a concern that the sensitivity of the resin composition will decrease due to the interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof 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%. As a method for maintaining the water content, adjusting the humidity in the storage conditions and reducing the porosity of the storage container can be cited.

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 with a filter; lining polytetrafluoroethylene or the like in an apparatus to perform distillation under conditions that suppress contamination as much as possible.

When the curable resin composition of the present invention is used as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm from the viewpoint of wiring corrosion. 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 further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

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

<Preparation of hardening resin composition> The hardening 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 previously known method.

Furthermore, in order to remove foreign matter such as dust or particles in the curable resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. On the other hand, from the perspective of productivity, 5 μm or less is more preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be pre-cleaned with an organic solvent. In the filtering step of the filter, multiple filters may be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can also be performed after pressurization. When filtering is performed after pressurization, the pressure of pressurization is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is preferred, 0.03MPa or more and 0.9MPa or less is more preferred, and 0.05MPa or more and 0.7MPa or less is further preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal 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.

<Application of the curable resin 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 of a semiconductor device or a stress buffer film, etc.

(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 explained.

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 may be laminated in two or more layers, and further laminated in 3 to 7 layers to form a laminate. The laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. Furthermore, the laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between any of the cured films. For example, a laminate having a layered structure in which at least three layers, namely, a first cured film, a metal layer, and a second cured film, are laminated in sequence can be preferably cited. The first cured film and the second cured film are both cured films of the present invention. For example, the first cured film and the second cured film are both films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form the second cured film may be the same composition or different compositions, but from the perspective of manufacturing suitability, the same composition is preferred. 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 devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include sealing films, substrate materials (base films or cover films, interlayer insulating films for flexible printed circuit boards), or insulating films for actual mounting purposes such as those mentioned above that are etched to form patterns. For such applications, for example, see Science & Technology Co., Ltd., "Advanced Functionality and Application Technology of Polyimide," April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, "Basics and Development of Polyimide Materials," November 2011, Japan Polyimide/Aromatic Polymer Research Society, "Latest Polyimide: Fundamentals and Applications," NTS, August 2010, etc.

Furthermore, the cured film of the present invention can also be used in the manufacture of offset printing plates or screen plates, the use of etching forming components, the manufacture of protective varnishes and dielectric layers in electronics, especially microelectronics, etc.

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 step 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 film forming step, and further includes an exposure step of exposing the film and a development step of developing the film (developing the film). Furthermore, the method for producing a cured film of the present invention preferably includes the film forming step (and the development step as required), and further includes a heating step of heating the film at 50 to 450°C. Specifically, it is also preferred to include the following steps (a) to (d). (a) A film forming step of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (b) An exposure step of exposing the film after the film forming step (c) A developing step of developing the exposed film (d) A heating step of heating the developed film at 50 to 450°C By heating in the heating step, the developed curable resin composition layer can be further cured. In the heating step, for example, the hot alkali generating agent is decomposed, thereby obtaining 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. Regarding the method for manufacturing a laminated body of the present embodiment, after forming a cured film according to the above-mentioned method for manufacturing a cured film, step (a) or steps (a) to (c) or steps (a) to (d) are performed again. In particular, it is preferred to perform the above-mentioned steps in sequence a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). 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 or between the cured films or at these two locations. In addition, in the manufacture of the laminate, it is not necessary to repeat all steps (a) to (d), and the laminate of the cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times as described above.

<Film-forming step (layer-forming step)> The manufacturing method of a preferred embodiment of the present invention includes a film-forming step (layer-forming step) 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, and examples thereof 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 addition, a bonding layer or an oxide layer may be provided on the surface of the substrate. In the present invention, a semiconductor substrate is particularly preferred, and a silicon substrate, a Cu substrate, and a mold substrate are more preferred. In addition, as a substrate, for example, a plate-shaped substrate (substrate) is used. The shape of the substrate is not particularly limited, and can be circular or rectangular, but a rectangular shape is preferred. On the surface of the substrate, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like can be provided. As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a hardening resin composition layer is formed on the surface of a resin layer such as a hardening resin composition layer or on the surface of a 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, as applicable methods, there can be exemplified 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 desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. When using the spin coating method, for example, it can be applied at a speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. Depending on the viscosity of the resin composition and the film thickness to be set, it is also preferred to apply at a speed of 300 to 3,500 rpm for 10 to 180 seconds. Furthermore, in order to obtain uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method of transferring the coating formed by pre-applying the above-mentioned applying method to the pseudo support body to the substrate can also be applied. Regarding the transfer method, the present invention can also preferably adopt the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592. Furthermore, a step of removing the excess film at the end of the substrate can be performed. Examples of such steps include edge bead rinsing (EBR), air knife, back rinse, etc. A pre-wetting step may also be used, in which various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate, and then the resin composition is applied.

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

<Exposure step> The manufacturing method of the present invention may also include an exposure step of exposing the above-mentioned film (hardening resin composition layer). There is no particular limitation on the exposure amount as long as the hardening resin composition can be hardened. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated as the exposure energy at a wavelength of 365 nm.

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

Regarding the exposure wavelength, if we explain it in relation to the light source, we can cite (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 light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. The curable resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays. This can achieve particularly high exposure sensitivity. From the perspective of handling and productivity, a wide (three wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred.

<Developing step> The manufacturing method of the present invention may also include a developing step of developing the exposed film (hardening resin component layer). By developing, the unexposed portion (non-exposed portion) is removed. As long as the desired pattern can be formed, there is no particular limitation on the developing method, such as spitting developer from a nozzle, spraying with a sprayer, and immersing the substrate in the developer, etc., preferably using the spitting from the nozzle. In the developing step, the step of continuously supplying the developer to the substrate, the step of keeping the developer in a substantially stationary state on the substrate, the step of vibrating the developer using ultrasound, etc., and the step of combining the above steps, etc. can be adopted.

Development is performed using a developer. If the curable resin composition is a negative curable resin composition, a developer in which the unexposed portion (non-exposed portion) of the curable resin composition layer is removed can be used without particular restrictions, and if the curable resin composition of the present invention is a positive curable resin composition, a developer in which the exposed portion (exposed portion) is removed can be used without particular restrictions. In the present invention, the use of an alkaline developer as a developer is referred to as alkaline development, and the use of a developer containing 50% by mass or more of an organic solvent as a developer is referred to as solvent development.

In alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total mass of the developer. It is particularly preferred that the developer contains no organic solvent. The developer in alkaline development is preferably an aqueous solution having a pH of 9 to 14. As the alkaline compound contained in the developer in alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia or amine can be cited. As amines, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. can be cited. Among them, alkaline compounds that do not contain metal are preferred, and ammonium compounds are more preferred. The alkaline compound may be only one or more than two. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.3 to 3 mass % in the total mass of the developer.

In solvent development, the developer preferably contains 90% or more of an 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 by inputting a structural formula as a calculated value in ChemBioDraw.

As for the organic solvent, 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 base solvent include cellulose 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., and examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, etc., and examples of sulfoxides include dimethyl sulfoxide.

In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. The developer may also contain other components. As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

[Developer supply method] There are no particular restrictions on the developer supply method as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate for rotary immersion development, or continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include vertical nozzles, shower nozzles, and mist nozzles. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, a method of supplying developer using a vertical nozzle or a method of continuously supplying developer using a spray nozzle is preferred. From the perspective of developer permeability to the image portion, a method of supplying developer using a spray nozzle is more preferred. In addition, after continuously supplying developer using a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the substrate is continuously supplied using a vertical nozzle again, and then the substrate is rotated to remove the developer from the substrate. This step may also be repeated multiple times. In addition, as a method for supplying the developer in the developing step, there can be adopted a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially static state on the substrate, a step of vibrating the developer on the substrate using ultrasound or the like, and a step combining these.

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. Alternatively, 100% by mass of the developer may be an organic solvent.

The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during the developing process is not particularly limited, but can usually be carried out at 10 to 45°C, preferably 20 to 40°C.

After the treatment with the developer, further rinsing may be performed. Alternatively, a method may be adopted in which a rinsing solution is supplied before the developer in contact with the pattern is completely dried. In the case of solvent development, it is preferred to use an organic solvent different from the developer for rinsing. As rinsing solutions for solvent development, PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropyl alcohol), etc. can be cited, and PGMEA is preferred. In the case of alkaline development, it is preferred to use pure water for rinsing. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinse liquid during rinsing is not particularly limited, and can preferably be performed at 10 to 45°C, more preferably at 18 to 30°C.

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as 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.)), alkyl 3-alkoxy propionates (e.g., 3-alkyl 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2-methyl The ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., can be preferably exemplified.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinse liquid contains an organic solvent, preferably 50 mass % or more of the rinse liquid is the organic solvent, more preferably 70 mass % or more of the rinse liquid is the organic solvent, and even more preferably 90 mass % or more of the rinse liquid is the organic solvent. Alternatively, 100 mass % of the rinse liquid may be the organic solvent.

The rinse solution may also contain other components. As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

[Method for supplying rinse liquid] There are no particular restrictions on the method for supplying rinse liquid as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, performing immersion development on the substrate, supplying the rinse liquid to the substrate in a spraying manner, and continuously supplying the developer to the substrate by a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure by a vertical nozzle, and it is more preferably a step of supplying the rinsing liquid by a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, it is possible to adopt a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a step combining these.

<Heating step> The manufacturing method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450°C. It is preferred to include a heating step after the film formation step (layer formation step), the drying step, and the development step. The curable resin composition of the present invention contains polymerizable compounds other than the specific resin, but in this step, unreacted polymerizable compounds other than the specific resin can be cured and unreacted polymerizable groups in the specific resin can be cured. Furthermore, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal alkali generator, in the heating step, for example, the thermal alkali generator is decomposed to generate a base, thereby causing the polyimide precursor to undergo a cyclization reaction. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or more is preferred, 80°C or more is more preferred, 140°C or more is further preferred, 150°C or more is particularly preferred, 160°C or more is further preferred, and 170°C or more is optimal. As the upper limit, 450°C or less is preferred, 350°C or less is more preferred, 250°C or less is further preferred, and 220°C or less is particularly preferred.

Regarding heating, it is preferred that the heating rate be 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, productivity can be ensured and excessive volatilization of amine can be prevented, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when 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 not clear, but it is believed that the reason is that the polymerizable groups in the specific resin between the layers undergo crosslinking reactions by setting the temperature to this level.

Heating can be performed in stages. As an example, the following pretreatment step can be performed, that is, the temperature is raised from 25°C to 180°C at 3°C/min and maintained at 180°C for 60 minutes, and the temperature is raised from 180°C to 200°C at 2°C/min and maintained at 200°C for 120 minutes. The heating temperature of the pretreatment step is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating ultraviolet rays. By means of such pretreatment steps, the properties of the membrane can be improved. The pretreatment step 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 step of more than two stages, for example, pretreatment step 1 can be carried out in the range of 100 to 150°C, and then pretreatment step 2 can be carried out in the range of 150 to 200°C.

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

In terms of preventing the decomposition of specific resins, it is better to conduct the heating process in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon during the heating step. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating mechanism is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, etc.

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

The metal layer is not particularly limited, and existing metals can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals. 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 a combination of 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.

As an example of the thickness of the metal layer, the thickest part may be 0.01 to 100 μm, preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

<Lamination step> The manufacturing method of the present invention preferably also includes a layering step.

The lamination step includes a series of steps including (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step, which are performed again in order on the surface of the hardened film (resin layer) or metal layer. Among them, it can be a state in which only (a) film formation step is repeated. In addition, it can also be a state in which (d) heating step is performed at the end or in the middle of the lamination. That is, it can also be set as follows, that is, steps (a) to (c) are repeated a predetermined number of times, and then (d) is heated, so that the layer of hardening resin composition layer that is layered is hardened. Furthermore, the (e) metal layer forming step may be included after the (c) developing step, and the heating of (d) may be performed each time, or the heating of (d) may be performed collectively after a predetermined number of layering steps. It is beyond doubt that the above-mentioned drying step and heating step may be further appropriately included in the layering step.

When a further layering step is performed after the layering step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified.

The above-mentioned lamination step is preferably performed 2 to 5 times, and more preferably performed 3 to 5 times. In addition, the layers in the lamination step can be the same in composition, shape, film thickness, etc., or different in composition, shape, film thickness, etc.

For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer in which the number of resin layers is 2 or more and 20 or less can be cited as an example, a structure in which the number of resin layers is 3 or more and 7 or less is preferred, and a structure in which the number of resin layers is 3 or more and 5 or less is further preferred.

<Surface activation treatment step> The method for producing a cured film of the present invention may include a surface activation treatment step of performing surface activation treatment on at least a portion of the metal layer and the photosensitive resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the exposure and development step and then after the photosensitive resin composition layer is subjected to the surface activation treatment step. The surface activation treatment may be performed only on at least a portion of the metal layer, only on at least a portion of the exposed photosensitive resin composition layer, or on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer and the resin layer disposed on the surface subjected to surface activation treatment can be improved. Specifically, the surface activation treatment includes plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after immersion in an aqueous hydrochloric acid solution to remove an oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

In the present invention, it is particularly preferred that the hardened film (resin layer) of the hardening resin composition is formed by further covering the metal layer after the metal layer is provided. Specifically, there can be cited an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are sequentially repeated, or an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, and (e) a metal layer forming step are sequentially repeated, and (d) a heating step is provided at the end or in the middle. By alternately performing the step of laminating the hardening resin composition layer (resin layer) and the step of forming the metal layer, the hardening resin composition layer (resin layer) and the metal layer can be alternately laminated.

The present invention also discloses a semiconductor device including 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 forming 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.

(Resin) The resin of the present invention preferably contains at least one selected from the group including the repeating unit represented by the above formula (2-1) and the repeating unit represented by the above formula (2-2). The resin of the present invention contains at least one selected from the group including the repeating unit represented by the above formula (2-1) and the repeating unit represented by the above formula (2-2). Except for this, the meaning and preferred embodiment are the same as those of the above-mentioned specific resin.

<Application> The resin of the present invention is preferably used as a resin included in a curable resin composition. In addition, in a composition using a conventional polyimide, such as an interlayer insulating film composition, there is no particular limitation, and a part or all of the conventional polyimide can be replaced with the resin of the present invention. Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is preferably used in a composition for forming an insulating film, a composition for forming a laminate, and other compositions for applications requiring chemical resistance. [Example]

The present invention is described in more 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 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 of specific resin) <Synthesis of diamine> [Synthesis of dinitro compound (A-1)] In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FFUJIFILM Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FFUJIFILM Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate, and the mixture was cooled to 5°C or less. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the addition was completed, the mixture was stirred at a temperature below 10°C for 30 minutes, and then the temperature was raised to 25°C and stirred for 3 hours. The reaction solution was then diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate, 300 mL of dilute hydrochloric acid, and saturated saline in that order. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, and then concentrated and vacuum dried using a distiller to obtain 61.0 g of a dinitro compound (A-1). The NMR spectrum confirmed that the compound was a dinitro compound (A-1). The dinitro compound (A-1) was analyzed by ¹ H-NMR. The results are shown below. ¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.97 (s, 3H), 4.55-4.57 (m, 2H), 4.70-4.73 (m, 2H), 5.63 (s, 1H), 6.16 (s, 1H), 9.16-9.17 (d, 2H), 9.24-9.25 (d, 1H) The following dinitro compounds (A-2) to (A-9) were synthesized in the same manner.

[Synthesis of diamine (AA-1)] 27.9 g (500 mmol) of reduced iron (manufactured by FFUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FFUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FFUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed into a flask equipped with a condenser and a stirrer, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour and stirred for 30 minutes. Next, the external temperature was raised to 85°C and stirred for 2 hours. After cooling to below 25°C, the mixture was filtered using CELITE (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. The mixture was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate water, and then washed with 300 mL of water and 300 mL of saturated saline water. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated using a distiller, and vacuum dried to obtain 11.0 g of diamine (AA-1). The NMR spectrum confirmed that the mixture was diamine (AA-1). ¹ H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H) In the same manner, using dinitro compounds (A-2) to (A-9) instead of dinitro compounds (A-1), diamines (AA-2) to (AA-9) of the following structures were synthesized. [Chemical formula 62] [Chemical formula 63] [Chemical formula 64]

<Synthesis of carboxylic acid dianhydride> In a flask equipped with a condenser and a stirrer, 18.5 g (0.88 mol) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 g of ethyl acetate and cooled to -10°C or below. Then, 10.6 g (40 mmol) of diamine (AA-1) and 7.12 g (90 mmol) of pyridine were dissolved in 60 g of ethyl acetate and added dropwise for 1 hour. After the addition, the mixture was stirred at a temperature of -10°C or below for 1 hour and at 25°C for 1 hour. Next, 500 mL of ethyl acetate and 300 mL of water were added and stirred for 10 minutes, then transferred to a separatory funnel, washed with 300 mL of water, washed twice with 200 mL of saturated sodium bicarbonate aqueous solution, and washed in that order with 200 mL of dilute hydrochloric acid aqueous solution and saturated saline solution. It was dried with magnesium sulfate, concentrated with a distiller, and the ethyl acetate solution was crystallized onto hexane. It was filtered and vacuum dried to obtain 20.0 g of anhydride (MA-1). It was confirmed to be anhydride (MA-1) from the NMR spectrum. The results of the analysis of anhydride (MA-1) by ¹ H-NMR are shown below. ¹ H-NMR data (deuterated dimethyl sulfoxide (DMSO), 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.88 (s, 3H), 4.44-4.47 (q, 2H), 4.60-4.62 (q, 2H), 5.70 (s, 2H), 6.06 (s, 1H), 8.23-8.26 (m, 4H), 8.52-8.54 (d, 2H), 8.65 (s, 2H), 8.82-8.83 (t, 1H), 10.98 (s, 2H) In the same manner, in the synthesis of anhydride (MA-1), diamines (AA-2) to (AA-7) were used instead of diamine (AA-1), thereby synthesizing anhydrides (MA-2) to (MA-7) having the following structures. In the synthesis of anhydride (MA-1), 4,4'-diaminobenzanilide was used instead of diamine (AA-1), thereby synthesizing anhydride (MA-8). In the synthesis of anhydride (MA-1), diamine (AA-10) having the following structure was used instead of diamine (AA-1), thereby synthesizing anhydride (MA-9). Diamine (AA-10) was synthesized by reacting diamine (AA-1) with 4-dinitrobenzanilic chloride to obtain dinitro form (A-10), and then reducing the dinitro form (A-10) by the same method as when synthesizing diamine (AA-1) from dinitro form (A-1). In the synthesis of anhydride (MA-1), diamine (AA-8) or (AA-9) was used instead of diamine (AA-1), thereby synthesizing (MA-10) and (MA-11) having the following structures, respectively. [Chemical formula 65] [Chemical formula 66] [Chemical formula 67] [Chemical formula 68] [Chemical formula 69]

<Synthesis of polyimide resin PI-1> In a flask equipped with a condenser and a stirrer, 11.0 g (18 mmol) of anhydride (MA-1) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 4.76 g (18 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-1. The molecular weight of PI-1 is Mw (weight average molecular weight) = 62,100, Mn (number average molecular weight) = 22,900. The structure of PI-1 is estimated to be represented by the following formula (PI-1). [Chemical formula 70]

<Synthesis of polyimide resin PI-2> In a flask equipped with a condenser and a stirrer, 9.73 g (18 mmol) of anhydride (MA-2) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 5.01 g (18 mmol) of diamine (AA-4) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 34.4 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-2. The molecular weight of PI-2 is Mw=74,200, Mn=29,000. The structure of PI-2 is estimated to be represented by the following formula (PI-2). [Chemical formula 71]

<Synthesis of polyimide resin PI-3> In a flask equipped with a condenser and a stirrer, 9.45 g (18 mmol) of anhydride (MA-3) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 8.27 g (18 mmol) of diamine (AA-6) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-3. The molecular weight of PI-3 is Mw=81,000, Mn=32,700. The structure of PI-3 is estimated to be represented by the following formula (PI-3). [Chemical formula 72]

<Synthesis of polyimide resin PI-4> In a flask equipped with a condenser and a stirrer, 11.0 g (18 mmol) of anhydride (MA-1) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 5.01 g (18 mmol) of diamine (AA-4) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-4. The molecular weight of PI-4 is Mw=81,000, Mn=32,700. The structure of PI-4 is estimated to be represented by the following formula (PI-4). [Chemical formula 73]

<Synthesis of polyimide resin PI-5> In a flask equipped with a condenser and a stirrer, 11.0 g (18 mmol) of anhydride (MA-1) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 3.75 g (18 mmol) of diamine (AA-7) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added for dilution. The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-5. The molecular weight of PI-5 is Mw=32,600, Mn=14,100. The structure of PI-5 is estimated to be represented by the following formula (PI-5). [Chemical formula 74]

<Synthesis of polyimide resin PI-6> In a flask equipped with a condenser and a stirrer, 15.31 g (18 mmol) of anhydride (MA-9) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 7.81 g (17 mmol) of diamine (AA-6) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 41.5 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-6. The molecular weight of PI-6 is Mw=28,400 and Mn=11,300. The structure of PI-6 is estimated to be represented by the following formula (PI-6). [Chemical formula 75]

<Synthesis of polyimide resin PI-7> In a flask equipped with a condenser and a stirrer, 11.5 g (18 mmol) of anhydride (MA-10) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 4.76 g (18 mmol) of diamine (AA-1) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1 liter of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide resin PI-7. The molecular weight of PI-7 is Mw (weight average molecular weight) = 35,500, Mn (number average molecular weight) = 13,900. The structure of PI-7 is estimated to be represented by the following formula (PI-7). [Chemical formula 76]

<Synthesis Example of Polyimide Precursor Resin PA-1> In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 g of diethylene glycol dimethyl ether while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) dissolved in 80 mL of N-methylpyrrolidone (NMP) was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain polyimide precursor PA-1. The molecular weight of the polyimide precursor PA-1 was Mw=30,600 and Mn=13,500. The structure of PA-1 is estimated to be a structure represented by the following formula (PA-1). [Chemical formula 77]

<Synthesis Example of Polyimide Precursor Resin PA-2> In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 g of diethylene glycol dimethyl ether while removing water. 8.56 g (75 mmol) of trifluoro-1-propanol, 3.25 g (25 mmol) of 2-hydroxyethyl methacrylate, and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) dissolved in 80 mL of N-methylpyrrolidone (NMP) was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain polyimide precursor PA-2. The molecular weight of the polyimide precursor PA-2 is Mw=28,300 and Mn=12,900. The structure of PA-2 is estimated to be represented by the following formula (PA-2). In formula (PA-2), * represents the bonding site of the oxygen atom bonded to R ^1. [Chemical formula 78]

<Synthesis Example of Polyimide Promotor Resin PA-3> In a flask equipped with a condenser and a stirrer, 12.5 g (45 mmol) of diamine (AA-4) and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 122 g of N-methylpyrrolidone (NMP) while removing water. Then, 28.2 g (45 mmol) of anhydride (MA-4) was added and stirred at 25°C for 5 hours. Next, after adding 40 g of N-methylpyrrolidone (NMP), the polyimide proto-driver resin was precipitated in 3 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide proto-driver resin was obtained by filtration, and was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide proto-driver resin was dried at 40° C. for 1 day under reduced pressure to obtain polyimide proto-driver PA-3. The molecular weight of the polyimide proto-driver PA-3 was Mw=50,300 and Mn=21,500. The structure of PA-3 is estimated to be represented by the following formula (PA-3). [Chemical formula 79]

<Synthesis Example of Polyimide Precursor Resin PA-4> In a flask equipped with a condenser and a stirrer, 29.3 g (47.8 mmol) of anhydride (MA-1) was suspended in 100 g of diethylene glycol dimethyl ether while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 9.37 g (45 mmol) of diamine (AA-7) dissolved in 80 mL of N-methylpyrrolidone (NMP) was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain polyimide precursor PA-4. The molecular weight of the polyimide precursor PA-4 is Mw=21,900 and Mn=10,100. The structure of PA-4 is estimated to be represented by the following formula (PA-4). [Chemical formula 80]

<Synthesis Example of Polyimide Precursor Resin PA-5> In a flask equipped with a condenser and a stirrer, 40.7 g (47.8 mmol) of anhydride (MA-9) was suspended in 180 g of diethylene glycol dimethyl ether while removing water. 16.4 g (100 mmol) of triethylene glycol monomethyl ether and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise for 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 50 mL of N-methylpyrrolidone (NMP) was added, and 11.89 g (45 mmol) of diamine (AA-1) dissolved in 100 mL of N-methylpyrrolidone (NMP) was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain polyimide precursor PA-5. The molecular weight of the polyimide precursor PA-5 is Mw=28,000 and Mn=13,500. The structure of PA-5 is estimated to be represented by the following formula (PA-5). [Chemical formula 81]

<Synthesis Example of Polyimide Precursor Resin PA-6> In a flask equipped with a condenser and a stirrer, 29.5 g (47.8 mmol) of anhydride (MA-11) was suspended in 100 g of diethylene glycol dimethyl ether while removing water. 4.61 g (100 mmol) of ethanol and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) dissolved in 80 mL of N-methylpyrrolidone (NMP) was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain polyimide precursor PA-6. The molecular weight of the polyimide precursor PA-6 is Mw=25,100 and Mn=10,500. The structure of PA-6 is estimated to be represented by the following formula (PA-6). [Chemical formula 82]

<Synthesis of Comparative Example Polyimide P-1> In a flask equipped with a condenser and a stirrer, 11.4 g (25 mmol) of anhydride (a-1) represented by the following formula (a-1) was dissolved in 33.1 g of N-methylpyrrolidone (NMP) while removing water. Then, 2.70 g (25 mmol) of 1,3-phenylenediamine (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and diluted by adding 50 g of N-methylpyrrolidone (NMP). The reaction solution was precipitated in 1.2 liters of methanol and stirred at 3,000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain comparative example polyimide P-1. The molecular weight of P-1 is Mw = 74,300, Mn = 30,100. The structure of P-1 is estimated to be represented by the following formula (P-1). P-1 does not have a polymerizable group at the position corresponding to L ¹¹ in formula (1-1), and therefore does not correspond to the specific resin. [Chemical formula 83] [Chemical formula 84]

<Synthesis of polyimide precursor P-2 for comparative example> In a flask equipped with a condenser and a stirrer, 21.8 g (47.8 mmol) of anhydride (a-1) was suspended in 100 g of diethylene glycol dimethyl ether while removing water. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were added successively, and stirred at 60°C for 5 hours. Then, after the mixture was cooled to -20°C, 11.9 g (100 mmol) of sulfinyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 4.87 g (45 mmol) of 1,3-phenylenediamine (Tokyo Chemical Industry Co., Ltd.) dissolved in 50 mL of NMP was added by dropwise addition for 1 hour. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 5 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure to obtain a comparative polyimide P-2. The molecular weight of the polyimide precursor P-2 was Mw=26,300 and Mn=12,100. The structure of P-2 is estimated to be a structure represented by the following formula (P-2). P-2 does not have a polymerizable group at the position corresponding to L ²¹ in formula (1-2), and therefore does not correspond to the specific resin. [Chemical Formula 85]

<Synthesis of polyimide precursor P-3 for comparative example> In a flask equipped with a condenser and a stirrer, 2.31 g (12.5 mmol) of 1,12-dodecanediamine, 1.41 g (5.7 mmol) of 4,4'-diaminodiphenylsulfone, and 5.0 g of N-methylpyrrolidone were added while removing water, and stirred at room temperature for 15 minutes. Then, a mixed solution of 10.00 g (19.1 mmol) of 1,10-(decamethylene)bis(trimellitic acid) dianhydride and 10.00 g of N-methylpyrrolidone was added for 15 minutes. After the addition was completed, the obtained mixed solution was heated to 60°C and stirred for 8 hours to obtain an NMP solution of the comparative polyimide precursor P-3. The solid content of the obtained solution was 40% by mass, and the Mw of P-3 was 42,000 and Mn = 20,000. P-3 does not have a polymerizable group at the position corresponding to L ²¹ in formula (1-2), and therefore does not correspond to the specific resin. [Chemical formula 86]

<Examples and Comparative Examples> In each example, the components listed in Table 1 below were mixed to obtain each hardening resin composition. In each comparative example, the components listed in Table 1 below were mixed to obtain each comparative composition. The hardening resin composition and the comparative composition obtained were pressure filtered through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Table 1, the values in the "mass parts" column represent the content (mass parts) of each component. In Table 1, for example, "PA-1/PI-1" in the "Type" column and "18/14" in the "Parts by Mass" column indicate that 18 parts by mass of PA-1 and 14 parts by mass of PI-1 were used, respectively. In addition, in Table 1, the entry "-" indicates that the corresponding component is not contained.

[Table 1] Resin Solvent Photopolymerization initiator Polymeric compounds Polymerization inhibitor Metal Adhesion Improver Migration inhibitors Onium salt or hot alkali generator Additives Hardening conditions Development method Development Resolution Drug resistance Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality Type Quality temperature Embodiment 1 PI-1 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180℃ Solvent A A B 2 PI-2 32 DMSO/GBL 60 OXE-01 1.2 SR-209 6.0 F-3 0.08 G-3 0.7 H-1 0.12 - - - - 180℃ Solvent B B A 3 PI-3 32 DMSO/GBL 60 OXE-01 1.2 SR-209 6.0 F-1 0.08 G-1 0.7 H-1 0.12 - - - - 180℃ Solvent A B A 4 PI-4 32 DMSO/GBL 60 OXE-01 1.2 SR-231 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180℃ Solvent A A B 5 PI-5 32 NMP 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180℃ Solvent B B B 6 PI-6 32 NMP 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - J-1 0.1 180℃ Solvent B A A 7 PI-7 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-3 0.12 - - - - 180℃ Solvent B A B 8 PA-1/PI-1 18/14 DMSO/GBL 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 I-1 0.5 - - 200℃ Solvent A B A 9 P1-1 32 NMP 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 - - - - 180℃ Solvent A A B 10 PA-1 32 DMSO/GBL 60 OXE-01 1.2 SR-231 6.0 F-2 0.08 G-1 0.7 H-1 0.12 I-1 0.5 - - 200℃ Solvent A B B 11 PA-2 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-1 0.12 I-1 0.5 - - 200℃ Solvent B B B 12 PA-2 35 NMP/EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2/G-4 0.2/0.2 H-2 0.12 I-1 0.5 - - 180℃ Solvent A A B 13 PA-3 35 NMP 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 I-1 0.5 - - 200℃ Alkali A A B 14 PA-4 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-1 0.12 I-1 0.5 - - 200℃ Solvent B B A 15 PA-5 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-1 0.12 I-1 0.5 - - 200℃ Solvent A B A 16 PA-6 32 DMSO/GBL 60 OXE-01 1.2 ADPH 6.0 F-2 0.08 G-1 0.7 H-3 0.12 I-1 0.5 J-1 0.1 200℃ Solvent B A B Comparison Example 1 P-1 35 NMP/EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2/G-4 0.2/0.2 H-2 0.12 - - J-1 0.1 180℃ Solvent C C D 2 P-2 35 NMP/EL 60 OXE-01 0.7 SR-209 2.8 F-4 0.02 G-2/G-4 0.2/0.2 - - - - - - 180℃ Solvent C C C 3 P-3 35 NMP 60 OXE-02 1.2 ADPH 6.0 F-2 0.08 G-2 0.7 H-1 0.12 I-1 0.5 - - 200℃ Alkali B C D

The details of each ingredient listed in Table 1 are as follows.

[Resin (specific resin or comparative resin)] ･PI-1 to PI-7: Polyimide resins PI-1 to PI-7 synthesized in the above ･PA-1 to PA-6: Polyimide prodriver resins PA-1 to PA-6 synthesized in the above ･P-1 to P-3: Comparative polyimide P-1 and comparative polyimide prodrivers P-2 to P-3 synthesized in the above

[Solvent] ･DMSO: dimethyl sulfoxide ･GBL: γ-butyrolactone ･EL: ethyl lactate ･NMP: N-methylpyrrolidone In Table 1, DMSO/GBL means that DMSO and GBL were mixed at a ratio of DMSO:GBL = 20:80 (mass ratio) and used. In Table 1, NMP/EL means that NMP and EL were mixed at a ratio of NMP:EL = 80:20 (mass ratio) and used.

[Photopolymerization initiator] ･OXE-01: IRGACURE OXE 01 (manufactured by BASF) ･OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compounds] ･SR-209: SR-209 (manufactured by Sartomer Company, Inc.) ･SR-231: SR-231 (manufactured by Sartomer Company, Inc.) ･ADPH: Dipentatriol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)

[Polymerization inhibitor] ･F-1: 1,4-benzoquinone ･F-2: 4-methoxyphenol ･F-3: 1,4-dihydroxybenzene ･F-4: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Metal Adhesion Improver] ･G-1 to G-4: Compounds of the following structures. In the following structural formula, Et represents an ethyl group. [Chemical Formula 87]

[Migration inhibitor] ･H-1: 1H-tetrazole ･H-2: 1,2,4-triazole ･H-3: 5-phenyltetrazole

[Onium salt or thermal alkali generator] ･I-1: Compound with the following structure [Chemical formula 88]

[Additives] ･J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

＜Evaluation＞ [Evaluation of chemical resistance] Each hardening resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form 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 to form a hardening resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The entire surface of the curable resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/cm ² , and the exposed curable resin composition layer (resin layer) was heated at a heating rate of 10°C/min in a nitrogen atmosphere, and heated for 180 minutes at the temperature listed in the "Curing Conditions" column of Table 1, thereby obtaining a cured layer (resin layer) of the curable resin composition layer. The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: A mixture of 90:10 (mass ratio) of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The resin layer was immersed in the chemical solution at 75°C for 15 minutes, the film thickness before and after immersion was compared, and the dissolution rate (nm/minute) was calculated. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in the "Chemical Resistance" column of Table 1. It can be said that the smaller the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: Dissolution rate is less than 200nm/minute. B: Dissolution rate is 200nm/minute or more and less than 300nm/minute. C: Dissolution rate is 300nm/minute or more and less than 400nm/minute. D: Dissolution rate is 400nm/minute or more.

[Evaluation of developer solubility (developability)] The developer solubility evaluation was carried out as follows. Each hardening resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form 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 to obtain a hardening resin composition layer with a uniform thickness of 35μm on the silicon wafer. The hardening resin composition layer on the silicon wafer was exposed to an exposure energy of 500mJ/ ^cm2 by i-ray using a stepper (Nikon NSR 2005 i9C). The exposure was performed using a binary mask having a 1:1 line and space pattern with a width of 50 μm, a width of 70 μm, or a width of 100 μm. For the curable resin composition layer after the exposure, in the example where "Solvent" is recorded in the "Developing Method (Developer)" column of Table 1, the curable resin composition layer after the exposure was developed using cyclopentanone at 30°C as a developer, and rinsed with PGMEA (propylene glycol monomethyl ether acetate). In the example where "Alkaline" is written in the "Developing method (Developer)" column of Table 1, the exposed curable resin composition layer was developed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 30°C as a developer, and rinsed with ion-exchanged water. During exposure, a 1:1 line and space (L/S) pattern with a width of 100μm was used, and the minimum time required for dissolution of the unexposed part when the thickness of the curable resin composition layer was 35μm was set as the minimum developing time, and evaluation was performed according to the following evaluation criteria. It can be said that the shorter the minimum developing time, the better the solubility of the developer. The evaluation results are recorded in the "Developability" column of Table 1. -Evaluation criteria- A: The above-mentioned minimum developing time is within 30 seconds. B: The above minimum developing time is more than 30 seconds and less than 60 seconds. C: The above minimum developing time is more than 60 seconds and less than 120 seconds. D: The solution is not completely dissolved within 120 seconds.

[Resolution evaluation] In each embodiment or comparative example, a copper-clad laminate having a curable resin composition layer was prepared by the same method as the above-mentioned developer solubility evaluation, and exposure using a 1:1 line and space pattern (L/S pattern) with a width of 70μm or a width of 100μm was performed. The development time was set to a development time twice the minimum development time in the above-mentioned developer solubility evaluation. In addition, after the development treatment and rinsing treatment were performed in the same method as the above-mentioned developer solubility evaluation, the copper surface was observed in the dissolved part to confirm whether the resolution was completed. The dissolved part in the pattern of the cured film after development was measured at 27 points and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Resolution" column of Table 1. -Evaluation Criteria- A: All 50μm L/S patterns were analyzed. B: One or more of the 50μm patterns were not analyzed, and all 70μm L/S patterns were analyzed. C: One or more of the 70μm L/S patterns were not analyzed at all, and all 100μm L/S patterns were analyzed. D: One or more of the 100μm L/S patterns were not completely analyzed due to development residues, etc.

From the above results, it can be seen that the curable resin composition containing the specific resin of the present invention has excellent chemical resistance. The comparative compositions of Comparative Examples 1 to 3 do not contain the specific resin. It can be seen that the comparative compositions of Comparative Examples 1 to 3 have poor chemical resistance.

<Example 101> The curable resin composition described in Example 1 was spin-coated on the surface of the copper thin layer in the resin substrate having the copper thin layer formed on the surface so that the film thickness was 20 μm. The curable resin composition coated on the resin substrate was dried at 100°C for 2 minutes and then exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm and an exposure amount of 400 mJ/ ^cm2 through a mask of a square pattern (a square pattern with a length and width of 100 μm each, repeated 10 times), thereby producing a pattern with a square remaining. After exposure, the pattern was obtained by developing with cyclopentanone for 30 seconds and rinsing with PGMEA for 20 seconds. Then, the temperature was raised at a rate of 10°C/min in a nitrogen environment until the temperature was reached as described in the "hardening conditions" column of Example 1 in Table 1. The temperature was then heated for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer had excellent insulation properties. In addition, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

without.

without.

Claims (24)

A resin having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the following formula (1-2), and having a repeating unit represented by the following formula (2-1) as the repeating unit represented by the aforementioned formula (1-1) or having a repeating unit represented by the following formula (2-2) as the repeating unit represented by the aforementioned formula (1-2); In formula (1-1), R ¹¹ represents a tetravalent group having a plurality of amide bonds, and L ¹¹ represents a divalent linking group including a polymerizable group. In formula (1-2), R ²¹ is a tetravalent group having a plurality of amide bonds, and L ²¹ represents a divalent group including a polymerizable group. R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group. In formula (2-1), ^X1 and ^X2 each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, ^Y1 represents an organic group having 1 to 30 carbon atoms, ^Q1 represents an organic group having 1 to 30 carbon atoms, ^A1 represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, ^A2 represents a group containing a polymerizable group, ^R1 and ^R2 each independently represent a hydrogen atom or a monovalent organic group, and n1 and n2 each independently represent an integer greater than 1; In formula (2-2), ^X3 and X4 represent an integer greater than 1. ^{R 4} each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a cyclic, linear or branched aliphatic group having 2 to 30 carbon atoms, Y ² represents an organic group having 1 to 30 carbon atoms, Q ² represents an organic group having 1 to 30 carbon atoms, A ³ represents a group containing at least one group selected from the group consisting of a polymerizable group, an aliphatic hydrocarbon group and a polyalkylene oxide group, A ⁴ represents a group containing a polymerizable group, R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group, G ¹ and G ² each independently represent an organic group having 1 to 30 carbon atoms, and n3 and n4 each independently represent an integer greater than 1. The resin as claimed in claim 1, wherein in the above formula (2-1), ^R1 and ^R2 each independently represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The resin as claimed in claim 1, wherein in the above formula (2-1), ^A1 represents a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group, a group containing a polyalkylene oxide group, or a group represented by formula (P-4), In formula (P-4), ^L4 represents a single bond or an m+1 valent linking group, ^A4 represents an alkyl group, a polyalkylene oxide group or a group represented by such a bond, m represents an integer greater than 1, and * represents a bonding site with ^Y1 . The resin as claimed in claim 1, wherein in the above formula (2-1), ^Y1 represents a group represented by formula (Y-1), In formula (Y-1), ^RY1 , ^RY2 and ^RY3 each independently represent a structure represented by any one of the following formulas (Y1-1) to (Y1-4), ^Z1 and ^Z2 each independently represent an amide bond, a and b each independently represent an integer greater than 0, at least one of ^RY1 , ^RY2 and ^RY3 in formula (Y-1) represents a bonding site with ^A1 in formula (2-1), In formulas (Y1-1) to (Y1-4), * represents a bonding site to other structures, and # represents a bonding site to ^A1 in formula (2-1) or a bonding site to a hydrogen atom. In formula (Y1-1) or (Y1-2), L ^Y1 and L ^Y2 each independently represent an alkylene group. In formula (Y1-3) or (Y1-4), L ^Y4 each independently represents a single bond or a divalent hydrocarbon group. In formula (Y1-4), L ^Y3 is a single bond or 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- , -NHC(=O)-, or a group obtained by combining two or more of them. In formula (Y1-3) or formula (Y1-4), n independently represents an integer of 1 to 4. The resin as claimed in claim 3 or claim 4, wherein in the above formula (2-1), ^R1 and ^R2 each independently represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The resin as claimed in claim 2 or claim 4, wherein in the above formula (2-1), ^A1 represents a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group, a group containing a polyalkylene oxide group, or a group represented by formula (P-4), In formula (P-4), ^L4 represents a single bond or an m+1 valent linking group, ^A4 represents an alkyl group, a polyalkylene oxide group or a group represented by such a bond, m represents an integer greater than 1, and * represents a bonding site with ^Y1 . The resin as described in claim 2 or claim 4, wherein in the above formula (2-1), ^A1 is a group represented by the following formula (P-2), formula (P-3) or formula (P-4), ^{and A2} is a group represented by the following formula (P-2) or formula (P-3); in the above formula (2-2), ^A3 is a group represented by the following formula (P-2), formula (P-3) or formula (P-4), and ^A4 is a group represented by the following formula (P-2) or formula (P-3), In formula (P-2), A ² represents a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group, or an alkoxymethyl group, and * represents a bonding site with Y ¹ , Q ¹ , Y ² , or Q ^2. In formula (P-3), A ² represents a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group, or an alkoxymethyl group, and L ² represents a alkyl group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, or -NR ^N -, carbonate bond, urea bond or a group obtained by bonding two or more of these bonds, Z ¹ represents an ether bond, ester bond, urethane bond, urea bond, carbonate bond or amide bond, * represents the bonding site with Y ¹ , Q ¹ , Y ² or Q ² , ^RN is a hydrogen atom or a hydrocarbon group, In formula (P-4), ^L4 represents a single bond or an m+1 valent linking group, ^A4 represents an alkyl group, a polyalkylene oxide group or a group represented by such a bond, m represents an integer greater than 1, and * represents a bonding site with ^Y1 . The resin as described in claim 3, wherein ^L4 in the above formula (P-4) is an ester bond, an amide bond, a urea bond or a urethane bond. The resin as claimed in claim 2 or claim 3, wherein in the above formula (2-1), ^Y1 represents a group represented by formula (Y-1), In formula (Y-1), ^RY1 , ^RY2 and ^RY3 each independently represent a structure represented by any one of the following formulas (Y1-1) to (Y1-4), ^Z1 and ^Z2 each independently represent an amide bond, a and b each independently represent an integer greater than 0, at least one of ^RY1 , ^RY2 and ^RY3 in formula (Y-1) represents a bonding site with ^A1 in formula (2-1), In formulas (Y1-1) to (Y1-4), * represents a bonding site to other structures, and # represents a bonding site to ^A1 in formula (2-1) or a bonding site to a hydrogen atom. In formula (Y1-1) or (Y1-2), L ^Y1 and L ^Y2 each independently represent an alkylene group. In formula (Y1-3) or (Y1-4), L ^Y4 each independently represents a single bond or a divalent hydrocarbon group. In formula (Y1-4), L ^Y3 is a single bond or 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- , -NHC(=O)-, or a group obtained by combining two or more of them. In formula (Y1-3) or formula (Y1-4), n independently represents an integer of 1 to 4. The resin as described in claim 4, wherein in the above formula (Y-1), a and b are 0 or 1. The resin as claimed in claim 4, wherein in the above formula (Y-1), ^RY1 , ^RY2 and ^RY3 are independently structures represented by the above formula (Y1-3). The resin as described in claim 4, wherein in the above formula (Y1-3), L ^{and Y4} are both single bonds. The resin as described in any one of claim 1 to claim 4, claim 8, and claim 10 to claim 12, wherein in the above formula (2-1), n1 is 1, n2 is 1, and in the above formula (2-2), n3 is 1, n4 is 1. The resin as described in any one of claims 1 to 4, claim 8, and claims 10 to 12, wherein ^X1 and ^X2 in the above formula (2-1) are independently an aromatic hydrocarbon group having 6 to 30 carbon atoms, and ^X3 and ^X4 in the above formula (2-2) are independently an aromatic hydrocarbon group having 6 to 30 carbon atoms. The resin as described in any one of claims 1 to 4, claim 8, and claims 10 to 12, wherein ^Y1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Y2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group. The resin as described in any one of claim 1 to claim 4 and claim 8, wherein ^Q1 in the above formula (2-1) is a group containing an aromatic hydrocarbon group, and ^Q2 in the above formula (2-2) is a group containing an aromatic hydrocarbon group. The resin as described in any one of claims 1 to 4, 8, and 10 to 12, wherein ^Q1 in the above formula (2-1) and ^Q2 in the above formula (2-2) are at least one structure selected from the group consisting of structures represented by the following formulas (A2-1) to (A2-5), In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group or a halogenated alkylene group, and at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R A224 , R ^A231 to R A238 , R ^A241 to R A248 and R A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated ^alkyl group or a halogenated alkylene group. At least one of ^A238 , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 may be a bonding site with ^A2 in the above formula (2-1) or ^A4 in the above formula (2-2), and * each independently represents a bonding site with other structures. The resin as described in any one of claim 17, wherein ^Q1 in the above formula (2-1) and ^Q2 in the above formula (2-2) are structures represented by the above formula (A2-1). A resin as described in any one of claims 1 to 4, 8, and 10 to 12, wherein the total content of the repeating units represented by formula (1-1) and the repeating units represented by formula (1-2) in the above-mentioned resin is 50 mass% or more relative to the mass of the above-mentioned resin. The resin as described in any one of claims 1 to 4, claim 8, and claims 10 to 12 has a repeating unit represented by formula (1-1), and the content of the repeating unit represented by formula (1-1) is greater than 70 mol% relative to the total repeating units of the above-mentioned resin. The resin as described in any one of claims 1 to 4, claim 8, and claims 10 to 12 has a repeating unit represented by formula (1-2), and the content of the repeating unit represented by formula (1-2) is greater than 70 mol% relative to the total repeating units of the above-mentioned resin. The resin as described in any one of claims 1 to 4, claim 8, and claims 10 to 12, wherein the weight average molecular weight is 10,000 to 100,000. The resin as described in any one of claims 1 to 4, 8, and 10 to 12, wherein the acid value is 0 to 2.0 mmol/g. The resin as described in any one of claims 1 to 4, 8, and 10 to 12, wherein the molar amount of polymerizable groups contained in 1 g of the resin is 0.05 to 10 mmol/g.