Photosensitive resin composition, cured product, laminate, method for producing the cured product, and semiconductor device

Abstract

To provide a cured product which is excellent in adhesion to a metal layer and is obtained by curing a photosensitive resin composition.SOLUTION: There are provided: a photosensitive resin composition which contains at least one resin selected from the group consisting of polyimides, polyamide-imides, polyimide precursors, and polyamide-imide precursors, and a photopolymerization initiator, the resin having a group capable of photodimerization reaction; a cured product obtained by curing the photosensitive resin composition; a laminate including the cured product; a method for producing the cured product; and a semiconductor device including the cured product or the laminate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured product, a laminate, a method for producing the cured product, and a semiconductor device. [Background technology]

[0002] Polyimide or polyamideimide has excellent heat resistance and insulating properties, and is therefore used in a variety of applications. While the applications are not particularly limited, examples include insulating films, sealing materials, and protective films for semiconductor devices used for packaging. Polyimide or polyamideimide is also used as a base film or coverlay for flexible substrates.

[0003] For example, in the above-mentioned applications, polyimide or polyamideimide is used in the form of a photosensitive resin composition containing at least one resin selected from the group consisting of polyimide, polyimide precursor, polyamideimide, and polyamideimide precursor. Such a photosensitive resin composition can be applied to a substrate by, for example, coating to form a resin film, and then, if necessary, exposed to light, developed, heated, etc., to form a cured product on the substrate. The polyimide precursor and the polyamideimide precursor are cyclized, for example, by heating, to become polyimide and polyamideimide, respectively, in the cured product. Since the photosensitive resin composition can be applied by a known coating method or the like, it can be said to have excellent adaptability in manufacturing, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the photosensitive resin composition when it is applied. In addition to the high performance of polyimide, polyamideimide, etc., from the viewpoint of such excellent adaptability in manufacturing, there are increasing expectations for the industrial application and development of the above-mentioned photosensitive resin composition.

[0004] For example, Patent Document 1 describes a liquid crystal aligning agent for photo-alignment, which contains at least two polymers that are reaction products from raw materials containing tetracarboxylic dianhydride and diamine; the polymers include specific polymer (A) and polymer (B); the raw materials used to synthesize polymer (A) contain at least one compound having a photoreactive structure and do not contain the specific compound; and the raw materials used to synthesize polymer (B) contain at least one specific compound and do not contain the compound having a photoreactive structure. Patent Document 2 describes a liquid crystal aligning agent characterized by containing a polymer having a specific structure in the side chain. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2018-180227 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-224273 Summary of the Invention [Problem to be solved by the invention]

[0006] It is desirable that the cured product obtained by curing the photosensitive resin composition has excellent adhesion to a metal layer.

[0007] The present invention aims to provide a photosensitive resin composition that can give a cured product that has excellent adhesion to metals, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. [Means for solving the problem]

[0008] Examples of typical embodiments of the present invention are given below. <1> At least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor; and a photopolymerization initiator, The resin has a group capable of undergoing photodimerization. Photosensitive resin composition. <2> the photodimerization reactive group is a group having a cinnamoyl structure; <1> The photosensitive resin composition according to claim 1. <3> The resin contains a radical polymerizable group. <1> or <2> The photosensitive resin composition according to claim 1. <4> Further containing a compound B having an alkoxysilyl group, <1> ~ <3> 1. The photosensitive resin composition according to claim 1 . <5> the compound B having an alkoxysilyl group has at least one group selected from the group consisting of a photodimerization reactive group and a radical polymerizable group; <4> The photosensitive resin composition according to claim 1. <6> The compound B having an alkoxysilyl group has an azole group. <4> or <5> The photosensitive resin composition according to claim 1. <7> The composition further includes a compound C having an azole group and at least one group selected from the group consisting of a radical polymerizable group and a photodimerization group. <1> ~ <6> 1. The photosensitive resin composition according to claim 1 . <8> Further included is a compound D having an azole group and not having an alkoxysilyl group, a radical polymerizable group, or a photodimerization reactive group. <1> ~ <7> 1. The photosensitive resin composition according to claim 1 . <9> Used to form an interlayer insulating film for a rewiring layer, <1> ~ <8> 1. The photosensitive resin composition according to claim 1 . <10> <1> ~ <9> 10. A cured product obtained by curing the photosensitive resin composition according to any one of the above items. <11> <10> 1. A laminate comprising two or more layers each made of the cured product according to claim 1, and a metal layer between any two adjacent layers made of the cured product. <12> <1> ~ <9> 10. A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of 1 to 3 on a substrate to form a film. <13> an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern, <12> A method for producing the cured product described in <14> The method further comprises, after the developing step, a second exposure step of exposing the pattern obtained by the developing step. <13> A method for producing the cured product described in <15> The film is heated at 50 to 450°C. <12> ~ <14> 10. A method for producing a cured product according to any one of the above. <16> <10> or a cured product according to <11> A semiconductor device comprising the stack described in claim 1. [Effects of the Invention]

[0009] According to the present invention, there are provided a photosensitive resin composition that can give a cured product that has excellent adhesion to metals, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for producing the cured product, and a semiconductor device including the cured product or the laminate. DETAILED DESCRIPTION OF THE INVENTION

[0010] The main embodiments of the present invention will be described below, but the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic" means either or both of "acrylic" and "methacrylic", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Unless otherwise specified, detection in GPC measurements is performed using a UV (ultraviolet) ray (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Furthermore, unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above," or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. As used herein, combinations of preferred embodiments are more preferred embodiments.

[0011] (Photosensitive resin composition) The photosensitive resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and a photopolymerization initiator, and the resin has a group capable of undergoing a photodimerization reaction. Hereinafter, at least one resin selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, which has a group capable of photodimerization reaction, will also be referred to as a "specific resin."

[0012] The photosensitive resin composition of the present invention may be either a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, but is preferably a negative-type photosensitive resin composition. A negative photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the unexposed portions (non-exposed portions) are removed by a developer. The positive photosensitive resin composition refers to a composition in which, when a layer formed from the photosensitive resin composition is exposed to light, the exposed portion (exposed area) is removed by a developer.

[0013] The cured product obtained from the photosensitive resin composition of the present invention has excellent adhesion to metals. The mechanism by which the above effects are obtained is unknown, but is speculated as follows.

[0014] The photosensitive resin composition of the present invention contains a resin having a photodimerization reactive group and a photopolymerization initiator. The inventors have found that by using such a resin, both polymerization by a photopolymerization initiator and dimerization of photodimerizable groups can be utilized for curing upon exposure to light, thereby forming strong bonds between the resins and providing excellent adhesion between the resulting cured product and metal. In particular, when at least one of the conditions of the resin having a polymerizable group or the photosensitive resin composition containing a crosslinking agent described below is satisfied, or when re-exposure is performed before heat curing after development, after heat curing, or during heating, it is believed that dimerization of photodimerization reactive groups in the resin is promoted, and adhesion to the metal is further improved. It is believed that the above-mentioned effects can be obtained in both positive and negative types by utilizing the re-exposure.

[0015] Furthermore, in conventional photosensitive resin compositions containing photopolymerization initiators, curing is sometimes insufficient, particularly on the surface of the film facing the air interface, resulting in poor chemical resistance. This is presumably because the polymerization does not proceed sufficiently on the air interface side due to the influence of oxygen or moisture. However, since the resin contained in the photosensitive resin composition of the present invention has a group capable of photodimerization, the photodimerization reaction proceeds on the surface of the film on the air interface side, and therefore the film is sufficiently cured even on the air interface side, and the resulting cured product is thought to have excellent chemical resistance. Because the cured product has excellent chemical resistance, it is thought that, for example, when a photosensitive resin composition containing a solvent is further applied to a cured product made of the photosensitive resin composition of the present invention and cured to produce a laminate, dissolution of the cured product is suppressed even if the cured product comes into contact with a developer or the photosensitive resin composition. According to the present invention, it is believed that a cured product having excellent chemical resistance can be obtained, in which the 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 is suppressed.

[0016] However, Patent Documents 1 and 2 do not describe a photosensitive resin composition containing a resin having a photodimerization reactive group and a photopolymerization initiator.

[0017] The components contained in the photosensitive resin composition of the present invention will be described in detail below.

[0018] <Specific resin> The photosensitive resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyamideimide, polyimide precursor, and polyamideimide precursor, and having a photodimerization reactive group. The photosensitive resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.

[0019] [Photodimerization Reaction Capable Group] The specific resin may have a photodimerization reactive group in the main chain or in the side chain of the resin, but preferably in the side chain. In this specification, the term "main chain" refers to the relatively longest bonded chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to any other bonded chain. The photodimerizable group is not particularly limited, but is preferably a group capable of undergoing a dimerization reaction by ultraviolet light. The photodimerizable group is preferably a group having a cinnamoyl structure, a coumarin structure, a naphthalene structure, or an anthracene structure, and more preferably a group having a cinnamoyl structure.

[0020] Moreover, the photodimerization reactive group is preferably a group represented by the following formula (P-1). [ka] In formula (P-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, j represents 1 or 2, R 1 each independently represents a monovalent organic group or a bonding site to another structure, and R 2 each independently represents a monovalent organic group or a bonding site to another structure, i represents an integer of 0 or more, i+j is 6 or less, and when j is 2, two T 1 may be the same or different, and when j is 2, two T 2 may be the same or different, and at least one of the structures contains a binding site to another structure.

[0021] In formula (P-1), R 1 R each independently represents a monovalent organic group or a bonding site to another structure. 1 When represents a monovalent organic group, it is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a biphenyl group. The hydrocarbon group may be substituted with a known substituent, such as a halogen atom or a cyano group. In formula (P-1), R 2 R each independently represents a monovalent organic group or a bonding site to another structure. 2 When represents a monovalent organic group, R 2is preferably a carboxy group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, or an arylcarbonyloxy group. The number of carbon atoms in the alkyl group in the alkylcarbonyloxy group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group in the alkenylcarbonyloxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4. The alkenyl group may be linear, branched, or cyclic. The aryl group in the arylcarbonyloxy group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. In formula (P-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T 1 is a hydrogen atom, and T 2 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (P-1), i represents an integer of 0 or more, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0. In formula (P-1), j represents 1 or 2, and is preferably 1.

[0022] The group represented by formula (P-1) contains at least one bonding site to another structure in the structure, and preferably contains only one bonding site to another structure in the structure. Also, R 2 At least one of R is preferably a binding site to another structure, 2 It is more preferable that one of them is a binding site with another structure. In addition, in the group represented by formula (P-1), all of R 2is a monovalent organic group, and R 1 An embodiment in which at least one of the above is a binding site to another structure is also one of the preferred embodiments of the present invention.

[0023] Furthermore, the specific resin preferably contains a structure represented by the following formula (P-2) as a structure containing a photodimerization reactive group. [ka] In formula (P-2), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, n represents 0 or 1, j represents 1 or 2, R 1 each independently represents a monovalent organic group or a bonding site to another structure, and R 2 each independently represents a monovalent organic group or a bonding site to another structure, i represents an integer of 0 or more, i+j is 6 or less, and when j is 2, T 1 may be the same or different, and when j is 2, there may be two or more T 2 may be the same or different, and two n's may be the same or different. In formula (P-2), T 1 , T 2 , R 1 , R 2 , i, and j are the same as those in the above formula (P-1). In formula (P-3), n is 0 or 1, and 0 is more preferable.

[0024] [Polymerizable group] The specific resin preferably has a polymerizable group. Examples of the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group, and an alkoxymethyl group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred.

[0025] Among these, the specific resin preferably contains a radical polymerizable group. When the specific resin has a radical polymerizable group, the photosensitive resin composition preferably contains a photoradical polymerization initiator described below as a photopolymerization initiator, more preferably contains a photoradical polymerization initiator described below and a radical crosslinking agent described below as a photopolymerization initiator, and even more preferably contains a photoradical polymerization initiator described below, a radical crosslinking agent described below, and a sensitizer described below as a photopolymerization initiator. From such a photosensitive resin composition, for example, a negative photosensitive layer is formed. The specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the photosensitive resin composition preferably contains a photoacid generator described later. From such a photosensitive resin composition, for example, a chemically amplified positive-type photosensitive layer or a negative-type photosensitive layer is formed.

[0026] [Polyimide precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2). Formula (2) [ka] In formula (2), A 1 and A 2 each independently represents an oxygen atom or -NH-; R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group.

[0027] The polyimide precursor used in the present invention preferably contains a photodimerizable group in the repeating unit represented by the above formula (2), and R 115 and R 111 It is more preferable that at least one of R 111 It is more preferable that the compound contains a group capable of undergoing a photodimerization reaction. Preferred embodiments of the photodimerization reaction capable group are as described above.

[0028] A in equation (2) 1 and A 2 each independently represents an oxygen atom or —NH—, and preferably an oxygen atom. R in Equation (2) 111 represents a divalent organic group. Examples of the divalent organic group include groups containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, and particularly preferred is a group represented by -Ar-L-Ar-. wherein each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2- or -NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

[0029] R 111 is preferably derived from a diamine. Examples of diamines used in producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine preferably contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

[0030] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof, 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 -SO2-, and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0031] Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-Phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-Diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 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 fluorene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine methyldisiloxane, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,At least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 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'-diaminoquaterphenyl may be mentioned.

[0032] Additionally, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598 are also preferred.

[0033] Also preferably used are diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of WO 2017 / 038598.

[0034] R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained organic film. Here, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0035] Also, R 111From the viewpoint of i-line transmittance, is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferably a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of the above is a fluorine atom, a methyl group or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom in formula (2). R 50 ~R 57 Examples of the monovalent organic group include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [ka] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

[0036] Also, R 111 may be a structure containing a photodimerization group. Preferred embodiments of the photodimerization group are as described above. For example, R 111 can also be a structure derived from a diamine compound having a photodimerization reactive group. R 111 When R contains a group capable of photodimerization, 111 It is preferable that the compound contains an aromatic hydrocarbon group and a structure in which the group containing the photodimerizable group is directly bonded to the aromatic hydrocarbon group. The aromatic hydrocarbon group is not particularly limited, but a benzene ring structure is preferred.

[0037] Also, R 111 When R contains the above photodimerization reactive group, 111 is preferably a structure represented by the following formula (LD-1). [ka] In formula (LD-1), Y D1 represents an (n+2)-valent group containing an aromatic hydrocarbon group, and P D1 represents a group having a photodimerization reactive group, n represents an integer of 1 or more, and * represents R 111 represents the bonding site with the nitrogen atom to which it is bonded.

[0038] -Y D1 - In formula (LD-1), Y D1 represents an (n+2) valent group containing an aromatic hydrocarbon group. Y D1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group in which three or more hydrogen atoms have been removed from a benzene ring. In formula (LD-1), Y D1 In the formula (1-1), it is preferable that the bonding sites to the two * in the formula (LD-1) are both aromatic hydrocarbon groups. 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above. In addition, in formula (LD-1), Y D1 In P D1Preferably, the bonding sites to P are all aromatic hydrocarbon groups. D1 is Y D1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above.

[0039] Y D1 preferably contains at least one structure selected from the group consisting of structures represented by the following formulas (A2-1) to (A2-5), and more preferably contains at least one structure selected from the group consisting of structures represented by the above formulas (A2-1) to (A2-5). [ka] In formulas (A2-1) to (A2-5), R A211 ~R A214 , R A221 ~R A224 , R A231 ~R A238 , R A241 ~R A248 and R A251 ~R A258 each independently represents a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxy group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represents 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; R A211 ~R A214 At least one of R A221 ~R A224 At least one of R A231 ~R A238 At least one of R A241 ~R A248 At least one of, and R A251 ~R A258 At least one of the above is P in the formula (1-1). 1 Each * independently represents a binding site to another structure.

[0040] Among these, Y 1 preferably contains a structure represented by any one of formulas (A2-1) to (A2-4), and more preferably contains a structure represented by either formula (A2-1) or formula (A2-4).

[0041] In formulas (A2-1) to (A2-5), R A211 ~R A214 , R A221 ~R A224 , R A231 ~R A238 , R A241 ~R A248 and R A251 ~R A258 does not contain a bonding site with the carbonyl group in the above formula (1-1), and R A211 ~R A214 At least one of R A221 ~R A224 At least one of R A231 ~R A238 At least one of R A241 ~R A248 At least one of, and R A251 ~R A258 At least one of the above is P in formula (LD-1). D1 It may also be a binding site to In formula (A2-1), R A211 ~R A214 P D1 If it is not a binding site for R A211 ~R A214 preferably each independently represent 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 hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and 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 more preferred, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferred. Above R A211 ~R A214The halogen atom in the halogenated alkyl group in the above formula (I) or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. In formula (A2-2), R A221 ~R A224 is R in formula (A2-1) A211 ~R A214 and preferred embodiments are also the same. In formula (A2-3), R A231 ~R A238 preferably 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 hydroxy group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, more preferably 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, and more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Above R A231 ~R A238 The halogen atom in the halogenated alkyl group in the above formula (I) or the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. In formula (A2-3), L A231 represents a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, -O-, -S-, -NR N It preferably represents -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, and more preferably represents a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O-, or a heterocyclic group, and more preferably represents a single bond or -O-. Above R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is preferably a divalent aromatic hydrocarbon group. The heterocyclic group is preferably, for example, a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, more preferably a group in which two hydrogen atoms have been removed from an aliphatic or aromatic heterocycle, and more preferably a group in which two hydrogen atoms have been removed from a ring structure such as a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, or morpholine ring. These heterocycles may further form a condensed ring with another heterocycle or a hydrocarbon ring. The heterocycle preferably has 5 to 10 ring members, and more preferably 5 or 6 ring members. The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom or a bromine atom being preferred. In formula (A2-4), R A241 ~R A248 , L A241 is R in formula (A2-3) A231 ~R A238 , L A231 and preferred embodiments are also the same. In formula (A2-5), R A251 ~R A258 is R in formula (A2-1) A211 ~R A214 and preferred embodiments are also the same.

[0042] In formula (A2-1), R A211 ~R A214 At least one of the groups represented by the formula (LD-1) is P D1 Preferably, the binding site is R A211 ~R A214 One of the above P D1 More preferably, the binding site is R A213 The above P D1 Preferably, the binding site is In formula (A2-2), R A221 ~R A224At least one of the groups represented by the formula (LD-1) is P D1 Preferably, the binding site is R A221 ~R A224 One of the above P D1 More preferably, the binding site is R A223 The above P D1 Preferably, the binding site is In formula (A2-3), R A231 ~R A238 At least one of the groups represented by the formula (LD-1) is P D1 Preferably, the binding site is R A231 ~R A238 Two of them are listed above. D1 More preferably, the binding site is R A231 ~R A234 One of them and R A235 ~R A238 One of the two is the above P D1 More preferably, R A231 and R A238 The two above are D1 It is particularly preferred that the binding site be In formula (A2-4), R A241 ~R A248 At least one of the groups represented by the formula (LD-1) is P D1 Preferably, the binding site is R A241 ~R A248 Two of them are listed above. D1 More preferably, the binding site is R A241 ~R A244 One of them and R A245 ~R A248 One of the two is the above P D1 More preferably, R A241 and R A248 The two above are D1 It is particularly preferred that the binding site be In formula (A2-5), R A251 ~R A258 At least one of the groups represented by the formula (LD-1) is P D1 Preferably, the binding site is R A251 ~RA258 Two of them are listed above. D1 More preferably, the binding site is R A251 ~R A254 One of them and R A255 ~R A258 One of the two is the above P D1 More preferably, R A253 and R A257 The two above are D1 It is particularly preferred that the binding site be

[0043] In formulas (A2-1) to (A2-5), it is preferable that each of the two * denotes * in formula (LD-1). That is, R 111 The two nitrogen atoms to which are bonded are preferably directly bonded to the positions represented by two * in formulae (A2-1) to (A2-5).

[0044] Among these, Y D1 is preferably a group represented by the following formula (Y-1) or (Y-2). [ka] In formula (Y-1), R Y11 , R Y12 , R Y13 are R in formula (A2-1), respectively. A211 , R A212 and R A214 The same applies to the preferred embodiments. In formula (Y-2), R Y21 ~R Y26 are R in formula (A2-4), respectively. A242 ~R A247 The same applies to the preferred embodiments. In formula (Y-1) or formula (Y-2), * represents R in formula (2). 111 The #s represent the bonding sites of the two nitrogen atoms to which the P in formula (LD-1) is bonded. D1 The binding sites for each are shown.

[0045] -P D1 - In formula (LD-1), P D1 represents a group having a photodimerization group. Preferred embodiments of the photodimerization group are the same as the preferred embodiments of the photodimerization group in the specific resin described above. PD1 is preferably a group represented by the following formula (PD-1). [ka] In formula (PD-1), L PD1 represents a single bond or an (m+1)-valent linking group, and X PD1 represents a photodimerization reactive group, m represents an integer of 1 or more, * represents Y in formula (LD-1). D1 represents the binding site with

[0046] In formula (PD-1), L PD1 is a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded is preferred, and a single bond, a hydrocarbon group, an ether bond, a carbonyl group, -NR N - or a group in which two or more of these are bonded together is more preferred. Above R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The above L PD1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group in which two or more hydrogen atoms have been removed from a benzene ring, or a group represented by a bond thereof.

[0047] In formula (PD-1), X PD1 The preferred embodiments of the photodimerization reactive group are the same as the preferred embodiments of the photodimerization reactive group in the specific resin described above.

[0048] In formula (PD-1), m is preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0049] -n- In formula (LD-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.

[0050] The structure represented by the above formula (LD-1) can be obtained, for example, as a structure derived from a diamine represented by the following formula (LDA-1). [ka] In the above formula (LDA-1), Y D1 , P D1 , n are the Y D1 , P D1 , n, and the preferred embodiments are also the same.

[0051] Also, R 111 may be a structure containing a polymerizable group. For example, R 111 can also be a structure derived from a diamine compound having a polymerizable group. The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound having an aromatic ring structure, and more preferably a compound having a structure in which a structure containing an amino group and a polymerizable group is directly bonded to the aromatic ring structure. The polymerizable group is preferably a group containing an ethylenically unsaturated bond, a cyclic ether group, a group containing a methylol group, or an alkoxymethyl group, more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or an alkoxymethyl group, and even more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group.

[0052] Also, R 111is a structure containing a polymerizable group, R 111 is preferably a structure represented by the following formula (1-1). [ka] In formula (1-1), Y 1 represents an (n+2)-valent group containing an aromatic hydrocarbon group, and P 1 represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents R 111 represents the bonding site with the nitrogen atom to which it is bonded.

[0053] -Y 1 - In formula (1-1), Y 1 represents an (n+2) valent group containing an aromatic hydrocarbon group. Y 1 The aromatic hydrocarbon group in is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring, and particularly preferably a group in which three or more hydrogen atoms have been removed from a benzene ring. In formula (1-1), Y 1 In the formula (1-1), it is preferable that the bonding sites to the two * in the formula (1-1) are both aromatic hydrocarbon groups. 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above. In addition, in formula (1-1), Y 1 In P 1 Preferably, the bonding sites to P are all aromatic hydrocarbon groups. 1 is Y 1 It is preferable that the aromatic hydrocarbon ring structure be directly bonded to the aromatic hydrocarbon ring structure contained in the above.

[0054] Y 1preferably contains at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5), and more preferably is at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5). However, in the explanation of the above formulas (A2-1) to (A2-5), "P in formula (LD-1)" D1 The description of "bonding site with P in formula (1-1)" is 1 This shall be read as "binding site with the In addition, Y 1 A preferred embodiment of the formula (LD-1) is Y D1 This is the same as the preferred embodiment of the above.

[0055] -P 1 - In formula (1-1), P 1 represents a group containing a polymerizable group. The polymerizable group is preferably a group containing an ethylenically unsaturated bond, a cyclic ether group, a group containing a methylol group, or an alkoxymethyl group, more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group, or an alkoxymethyl group, and even more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group. P 1 The number of polymerizable groups contained in is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0056] Also, P 1 is preferably a group represented by the following formula (P-1). [ka] In formula (P-1), L 1 represents a single bond or a linking group having a valence of (m+1), and A 2represents a polymerizable group, m represents an integer of 1 or more, * represents Y 1 represents the binding site with In formula (P-1), L 1 is a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded is preferred, and a single bond, a hydrocarbon group, an ether bond, a carbonyl group, -NR N - or a group in which two or more of these are bonded together is more preferred. Above R N is as described above. The above L 1 The hydrocarbon group in is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination thereof, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group in which two or more hydrogen atoms have been removed from a benzene ring, or a group represented by a bond thereof.

[0057] In formula (P-1), A 2 is preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group, and more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group.

[0058] In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

[0059] Also, P 1 is preferably a group represented by the following formula (P-2) or formula (P-3). [ka] In formula (P-2), A 2 represents a polymerizable group, and * represents Y 1represents the binding site with In formula (P-2), A 2 is A in formula (P-1) 2 The same applies to the preferred embodiments. In formula (P-3), A 2 represents a polymerizable group, and L 2 is a hydrocarbon group, or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N - or a group in which two or more of these are bonded together; Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents Y 1 R represents the binding site. N is as described above. In formula (P-3), A 2 is A in formula (P-1) 2 The same applies to the preferred embodiments. In formula (P-3), L 2 is preferably a hydrocarbon group, a (poly)alkyleneoxy group, or a group represented by a combination thereof. The hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group. In this specification, the term "(poly)alkyleneoxy group" refers to an alkyleneoxy group or a polyalkyleneoxy group. In addition, in the present invention, the term "polyalkyleneoxy group" refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. The aromatic hydrocarbon group 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 phenylene group or naphthylene group, and particularly preferably a phenylene group. The alkylene group in the (poly)alkyleneoxy group is 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 or propylene group, and even more preferably an ethylene group. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, still more preferably 2-5, and particularly preferably 2-4. In formula (P-3), Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferred. In the present invention, when simply referring to an "ester bond," "urethane bond," "amide bond," etc., the orientation of these bonds is not limited. 1 is an ester bond, Z 1 L in 2 The bonding site may be a carbon atom or an oxygen atom in the ester bond.

[0060] -n- In formula (1-1), n ​​represents an integer of 1 or more, preferably 1 to 10, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 1.

[0061] R in Equation (2) 115 represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * each independently represents a bonding site to another structure. [ka] In formula (5), R 112 represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, -NHCO-, or a group selected from combinations thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0062] R 115 Specifically, R may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. 115 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [ka] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of R in formula (2) 115 The same applies to the preferred range.

[0063] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2 ',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 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-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0064] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0065] In equation (2), R 111 and R 115At least one of R may have an OH group. 111 Examples of the amino acid residue include residues of bisaminophenol derivatives.

[0066] R in Equation (2) 113 and R 114 Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. 113 and R 114 Preferably, at least one of R contains a polymerizable group, and more preferably, both of R contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0067] [ka]

[0068] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201 Examples of the alkylene group include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene; 1,2-butanediyl, 1,3-butanediyl, -CHCH(OH)CH-; and polyalkyleneoxy groups. Of these, alkylene groups such as ethylene and propylene, -CHCH(OH)CH-, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

[0069] In equation (2), R 113 is a hydrogen atom, or R 114 When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0070] In equation (2), R 113 and R 114 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0071] The polyimide precursor preferably has fluorine atoms in its structure, and the fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0072] To improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as diamines.

[0073] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the width of the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, and R 111 and R 112 each independently represents a divalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 At least one of the groups is a group containing a polymerizable group, and it is preferred that both of the groups are groups containing a polymerizable group.

[0074] A 1 , A 2 , R 111 , R 113 and R 114 are each independently A in formula (2). 1 , A 2 , R 111 , R 113 and R114 The same applies to the preferred range. R 112 is R in Equation (5). 112 The same applies to the preferred range.

[0075] The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

[0076] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminal repeating units may be repeating units represented by formula (2).

[0077] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

[0078] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at least 0.1 g in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyimide that dissolves at least 0.5 g is preferred, and a polyimide that dissolves at least 1.0 g is more preferred. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less. In addition, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, the term "main chain" refers to the relatively longest bonded chain in the molecule of the polymer compound that constitutes the resin, and the term "side chain" refers to any other bonded chain.

[0079] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. The fluorine atom may be, for example, R in the repeating unit represented by formula (4) described later, or R 131 It is preferable that R132 in the repeating unit represented by formula (4) be described later, or R 131 It is more preferable that the alkyl group is contained as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

[0080] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains a silicon atom. The silicon atom is, for example, R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included. 131 It is more preferable that the organic modified (poly)siloxane structure described below is contained in the above. The silicon atom or the organically modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0081] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is represented by R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below 131 and R in the repeating unit represented by formula (4) described below is preferably included. 132 or R in the repeating unit represented by formula (4) described below 131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described below. 131 and R in the repeating unit represented by formula (4) described below is preferably included.131 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV):

[0082] [ka]

[0083] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

[0084] In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CHCH(OH)CH-, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

[0085] Among these, R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents R 21 represents the bonding site with the oxygen atom to which it is bonded. In the formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L are the same as those of the above-mentioned R 21 The preferred embodiments are the same as those of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in the above. In formula (R1), X is preferably an oxygen atom. In the formulae (R1) to (R3), * has the same meaning as * in the formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

[0086] In formula (IV), * represents a bonding site to another structure, and is preferably a bonding site to the main chain of the polyimide.

[0087] The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0088] -Polymerizable group other than a group having an ethylenically unsaturated bond- The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond. Examples of polymerizable groups other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group. The polymerizable group other than the group having an ethylenically unsaturated bond is, for example, R in the repeating unit represented by formula (4) described below. 131 It is preferred that the hydroxyl group is included in the formula (I). The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0089] -Polarity conversion group- The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is represented by R 113 and R 114 The acid-decomposable group is the same as that described above, and the preferred embodiments are also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described below. 131 , R 132 , contained in the terminals of polyimides, etc.

[0090] -Acid value- When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability. pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa is a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, values ​​listed in the "Revised 5th Edition Chemistry Handbook: Basics" edited by the Chemical Society of Japan may be referenced. Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

[0091] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group. The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group is, for example, R in the repeating unit represented by formula (4) described below. 132 or R in the repeating unit represented by formula (4) described below 131 It is preferred that the hydroxyl group is included in the formula (I). The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0092] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. In the case where the polymerizable group is present, the polymerizable group is R 131 and R 132 or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). Formula (4-1) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [ka] R 134 and R 135 At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group has the same meaning as in formula (4).

[0093] Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, and crosslinkable groups other than the above-mentioned group having an ethylenically unsaturated bond. R 131 represents a divalent organic group. The divalent organic group is R in formula (2). 111 The same examples are given, and the preferred ranges are also the same. Also, R 131 Examples of the diamine include a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cycloaliphatic, and aromatic diamines. Specific examples include R in the formula (2) of the polyimide precursor. 111 Examples include:

[0094] R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain, in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0095] Examples of diamines containing two or more ethylene glycol chains, two or more propylene glycol chains in one molecule include, but are not limited to, JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0096] R 132 represents a tetravalent organic group. The tetravalent organic group is R 115 The same examples are given, and the preferred ranges are also the same. For example, R 115 The four bonds of the tetravalent organic group exemplified by the following are bonded to the four -C(=O)- moieties in the above formula (4) to form a fused ring.

[0097] Also, R 132 The R 2 groups in the polyimide precursor are exemplified by tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. 115 From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0098] R131 and R 132 It is also preferable that at least one of R 131 Preferred examples of R include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18). 132 As such, the above (DAA-1) to (DAA-5) are more preferred examples.

[0099] The polyimide preferably has fluorine atoms in its structure, and the content of fluorine atoms in the polyimide is preferably 10% by mass or more and 20% by mass or less.

[0100] To improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0101] In order to improve the storage stability of the resin composition, it is preferable that the main chain terminals of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-8-aminonaphthalene. 2-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.

[0102] -Imidization rate (ring closure rate)- From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate (also referred to as the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak at 1377 cm due to the imide structure was observed. -1 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 P1 around 1377cm. -1 The peak intensity P2 around the peak intensity P1 is then measured. The imidization rate of the polyimide can be calculated using the obtained peak intensities P1 and P2 based on the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[0103] All polyimides are of the same type R 131 or R 132 and may contain a repeating unit represented by the above formula (4) containing two or more different types of R 131 or R 132 The polyimide may contain a repeating unit represented by the above formula (4), which includes: In addition to the repeating unit represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating unit represented by the above formula (2).

[0104] Polyimides can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent), or by completely imidizing the polyimide precursor using a known imidization reaction method, or by terminating the imidization reaction midway to introduce a partial imide structure, or by blending a fully imidized polymer with the polyimide precursor to introduce a partial imide structure. Other known polyimide synthesis methods can also be used.

[0105] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (for example, breaking elongation), the weight-average molecular weight is particularly preferably 15,000 or more. The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersity of the polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimides as a single resin are each within the above-mentioned ranges.

[0106] [Polyamide-imide precursor] The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, and R 111 represents a divalent organic group, and A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group. The polyamide-imide precursor is R 111 It is preferable that the compound has a group capable of undergoing photodimerization reaction.

[0107] In formula (PAI-2), R 117 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. A preferred example of the halogenated alkylene group is a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0108] Also, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides. Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0109] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0110] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydrides (for example, trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (for example, trimellitic anhydride chloride).

[0111] In formula (PAI-2), R 111 , A 2 , R 113 are the R in the above formula (2), 111 , A 2 , R 113 The same applies to the preferred embodiments.

[0112] The polyamideimide precursor may further comprise other repeating units. Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1). [ka]

[0113] In formula (PAI-1), R 116 represents a divalent organic group, and R111 represents a divalent organic group. In formula (PAI-1), R 116 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. A preferred example of the halogenated alkylene group is a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0114] Also, R 116is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound. The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

[0115] Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0116] Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and hexadecafluoroadipic acid. Examples of the carboxylic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedicarboxylic acid, heneicosanedicarboxylic acid, docosanedicarboxylic acid, tricosanedicarboxylic acid, tetracosanedicarboxylic acid, pentacosanedicarboxylic acid, hexacosanedicarboxylic acid, heptacosanedicarboxylic acid, octacosanedicarboxylic acid, nonacosanedicarboxylic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, and benzophenone-4,4'-dicarboxylic acid. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups in the specific examples of the dicarboxylic acid compound are halogenated.

[0117] In formula (PAI-1), R 111 is R in the above equation (2) 111 The same applies to the preferred embodiments.

[0118] The polyamideimide precursor preferably has fluorine atoms in its structure, and the fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

[0119] To improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, the polyamide-imide precursor may be copolymerized with bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as a diamine component.

[0120] In one embodiment of the polyamideimide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to this total content, and all repeating units in the polyamideimide precursor excluding the terminal repeating units may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to this total content, and all repeating units in the polyamideimide precursor except for the terminal repeating units may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0121] The polyamideimide precursor has a weight-average molecular weight (Mw) of preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more 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 even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyamideimide precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyamideimide precursors as a single resin are each within the above-mentioned ranges.

[0122] [Polyamide-imide] The polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or may be a polyamideimide that is soluble in a developer containing an organic solvent as a main component. In this specification, alkali-soluble polyamideimide refers to a polyamideimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyamideimide that dissolves 0.5 g or more is preferred, and a polyamideimide that dissolves 1.0 g or more is more preferred. There is no particular upper limit to the amount of dissolution, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

[0123] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, the polyamideimide preferably contains a fluorine atom. The fluorine atom can be, for example, R 117 , or R 111 and R in the repeating unit represented by formula (PAI-3) described below is preferably included.117 , or R 111 It is more preferable that the alkyl group is contained as a fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more and 20% by mass or less.

[0124] -Ethylenically unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamideimide may have an ethylenically unsaturated bond. The polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain. The ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is represented by R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 and R in the repeating unit represented by formula (PAI-3) described below is preferably included. 117 , or R 111 It is more preferable that the group having an ethylenically unsaturated bond is contained in the formula (I). Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.

[0125] The amount of ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0126] -Polymerizable group other than ethylenically unsaturated bond- The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the polyimide described above. The polymerizable group other than the ethylenically unsaturated bond is, for example, R in the repeating unit represented by formula (PAI-3) described later.111 It is preferred that the hydroxyl group is included in the formula (I). The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

[0127] -Polarity conversion group- The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is represented by R 113 and R 114 The acid-decomposable group is the same as that described above, and the preferred embodiments are also the same.

[0128] -Acid value- When the polyamideimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. Furthermore, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. The acid group contained in the polyamideimide may be the same as the acid group in the polyimide described above, and the preferred embodiments are also the same.

[0129] -Phenol hydroxy group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyamideimide preferably has a phenolic hydroxy group. The polyamideimide may have a phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group is, for example, R 117 , or R 111 It is preferred that the hydroxyl group is included in the formula (I). The amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

[0130] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 are R in formula (PAI-2), respectively. 111 and R 117 The same applies to the preferred embodiments. In the case where the polymerizable group is present, the polymerizable group is R 111 and R 117 or may be located at the end of the polyamideimide.

[0131] In order to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of the polyamideimide with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. Preferred embodiments of the terminal capping agent are the same as those of the terminal capping agent for the polyimide described above.

[0132] -Imidization rate (ring closure rate)- The imidization rate (also called "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less. The imidization rate is measured in the same manner as the ring closure rate of the polyimide.

[0133] The polyamideimide may contain repeating units represented by the above formula (PAI-3) all containing one type of R111 or R117, or may contain two or more different types of R 131 or R 132 The polyamideimide may contain a repeating unit represented by the above formula (PAI-3), which includes: In addition to the repeating unit represented by the above formula (PAI-3), the polyamideimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0134] Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by terminating the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

[0135] The weight-average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight-average molecular weight 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The polyamideimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersity of the polyamideimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple polyamideimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyamideimides as a single resin are each within the above-mentioned ranges.

[0136] [Method for producing polyimide precursors, etc.] The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing a polyimide precursor, etc., it is preferable 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 determined depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0137] -End-capping agent- In the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like to further improve storage stability. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of end-capping agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents. Furthermore, when capping the amino group at the resin terminal, it is possible to cap it with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0138] -Solid precipitation- The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain polyimide precursors and the like. To improve the degree of purification, the polyimide precursors and the like may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. Furthermore, the process may include a step of removing ionic impurities using an ion exchange resin.

[0139] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

[0140] The resin composition of the present invention also preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor having a structure derived from a dianhydride (R 115 ) preferably contains two or more kinds of polyimide precursors with different

[0141] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0142] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. In addition, a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low. In this embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0143] <Compounds containing an alkoxysilyl group> The photosensitive resin composition of the present invention preferably contains compound B, which is a compound having an alkoxysilyl group. Compounds that fall under the above-mentioned specific resins are not considered to fall under Compound B.

[0144] [Alkoxysilyl group] The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but from the viewpoints of pattern formability and adhesion of the cured product to metal, a trialkoxysilyl group is preferred. The alkoxy group in the alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably an ethoxy group.

[0145] [Photodimerization Reaction Capable Group] Compound B preferably has at least one group selected from the group consisting of a photodimerizable group and a radically polymerizable group, and more preferably has at least one group selected from the group consisting of a group having a cinnamoyl structure and a radically polymerizable group. The preferred embodiments of the photodimerization reaction group contained in the compound B are the same as the preferred embodiments of the photodimerization reaction group contained in the specific resin described above. The radical polymerizable group contained in compound B is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, with a (meth)acryloyloxy group being preferred.

[0146] [Formula (B1-1), Formula (B1-2)] Compound B is preferably a compound represented by the following formula (B1-1) or (B1-2). Furthermore, the compound represented by the following formula (B1-1) or (B1-2) is preferably a compound corresponding to the low molecular weight compound B described below. [ka] In formula (B1-1), R 1 each independently represents a monovalent organic group, n represents an integer of 0 to 5, T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group; X 1 represents a divalent linking group, Z 1 represents an alkoxysilyl group. In formula (B1-2), R 1 each independently represents a monovalent organic group, m represents an integer of 0 to 4, T 3 ~T 6 each independently represents a hydrogen atom or a monovalent organic group; X 2 and X 3 each independently represents a divalent linking group; Z 2 and Z 3 each independently represents an alkoxysilyl group.

[0147] In formula (B1-1), R 1 R each independently represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom. 1 When represents a monovalent organic group, it is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a biphenyl group. The hydrocarbon group may be substituted with a known substituent, such as a halogen atom or a cyano group. In formula (B1-1), n ​​represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 0. Also, when n is 1, R 1 is T 1 is preferably in the para position relative to the carbon atom to which it is bonded. In formula (B1-1), T 1 and T 2 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T1 is a hydrogen atom, and T 2 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (B1-1), X 1 represents a divalent linking group, and is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N - is preferably a group represented by a bond to at least one group selected from the group consisting of: Above R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, still more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. Also, X 1 is a group represented by the following formula (X-1): [ka] In formula (X-1), L X1 represents a single bond or a divalent linking group, A X -O- or -NR N - represents L X2 represents a divalent linking group, * represents T in formula (B1-1). 1 represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (B1-1). 1 represents the binding site with Above R N is as described above. In formula (X-1), L X1 is preferably a single bond or a hydrocarbon group, more preferably a single bond or an optionally substituted ethylene group, and even more preferably a single bond or an unsubstituted ethylene group. Substituents on the ethylene group include a cyano group and a halogen atom. In formula (X-1), A X Ha-NR N - is preferred, and -NH- is more preferred. In formula (X-1), L X2 represents a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR NA group represented by a bond to at least one group selected from the group consisting of - is preferred, a hydrocarbon group is more preferred, and an alkylene group is even more preferred. The number of carbon atoms in the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 3 to 6. In formula (B1-1), Z 1 The preferred embodiments of are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0148] In formula (B1-2), R 1 A preferred embodiment of the formula (B1-1) is R 1 This is the same as the preferred embodiment of the above. In formula (B1-2), T 3 ~T 6 each independently represents a hydrogen atom or a monovalent organic group, is preferably a hydrogen atom, a cyano group, or a halogen atom, and is more preferably a hydrogen atom. Also, T 1 and T 2 are all hydrogen atoms, or T 4 and T 5 is a hydrogen atom, and T 3 and T 6 An embodiment in which is a cyano group or a halogen atom is also one of the preferred embodiments. In formula (B1-2), X 2 and X 3 each independently represents a divalent linking group, and is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N - is preferably a group represented by a bond to at least one group selected from the group consisting of: Above R N is as described above. In formula (B1-2), X 2 and X 3 In another preferred embodiment, one or both of the following are groups represented by the above formula (X-1). However, X 2 is a group represented by the above formula (X-1), * in formula (X-1) represents T in formula (B1-2). 3represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (1-2). 2 represents the binding site with Also, X 3 is a group represented by the above formula (X-1), * in formula (X-1) represents T in formula (B1-2). 6 represents the bonding site with the carbon atom to which Z is bonded, and # represents the bonding site with the carbon atom to which Z is bonded in formula (B1-2). 3 represents the binding site with In formula (B1-2), Z 2 and Z 3 The preferred embodiments of the alkoxysilyl groups are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0149] [Azole group] It is also preferable that compound B has an azole group. According to the above embodiment, it is believed that the azole group coordinates with a metal such as copper, thereby further improving the adhesion of the cured product to the metal. The azole group in compound B may be a five-membered heterocyclic compound containing one or more nitrogen atoms as ring members, and may have a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent or a fused ring structure. However, it is preferably a five-membered heterocyclic compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members, and may have a structure in which one or more hydrogen atoms have been removed from a five-membered heterocyclic compound which may have a substituent. From the viewpoint of adhesion of the cured product to metal, the azole group is preferably a group having a structure in which one or more hydrogen atoms have been removed from a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a benzotriazole ring, or a tetrazole ring, and more preferably a group having a structure in which one or more hydrogen atoms have been removed from an imidazole ring, a benzimidazole ring, a 1,2,4-triazole ring, or a benzotriazole ring.

[0150] The azole group in compound B is preferably a group represented by the following formula (B-1) or (B-2). [ka] In formula (B-1), R B1 represents a bonding site to another structure, a hydrogen atom or a monovalent organic group, and Z B1 ~Z B4 are each independently, =CR B7 - or a nitrogen atom, R B7 represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, and R B1 and R B7 at least one of which represents a binding site with other structures; In formula (B-2), R B2 ~R B6 each independently represents a bonding site to another structure, a hydrogen atom, or a monovalent organic group; Z B5 and Z B6 are each independently, =CR B8 - or a nitrogen atom, R B8 represents a bonding site with another structure, a hydrogen atom, or a monovalent organic group, and R B2 ~R B6 and R B8 At least one of these represents a binding site with another structure.

[0151] In formula (B-1), R B1 represents a bonding site to another structure, a hydrogen atom or a monovalent organic group, and more preferably a bonding site to another structure. Above R B1 The monovalent organic group in is not particularly limited, and any known organic group can be used as long as the effects of the present invention can be obtained, but is preferably a hydrocarbon group or an amino group, and more preferably an alkyl group or an amino group. The number of carbon atoms in the hydrocarbon group or alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4. The amino group may be a substituted amino group or an unsubstituted amino group.

[0152] In formula (B-1), Z B1 ~Z B4are each independently, =CR B7 - or a nitrogen atom. Among them, Z B1 ~Z B4 Two of them are nitrogen atoms and two are =CR B7 -Z B1 ~Z B4 One of them is a nitrogen atom and three are =CR B7 -, or Z B1 ~Z B4 Three of them are nitrogen atoms and one is =CR B7 - is preferred. Among these, Z B1 and Z B3 is a nitrogen atom, and Z B2 and Z B4 GA=CR B7 -Z B1 and Z B2 is a nitrogen atom, and Z B3 and Z B4 GA=CR B7 -Z B2 is a nitrogen atom, and Z B1 , Z B3 and Z B4 GA=CR B7 -, or Z B1 , Z B2 and Z B3 is a nitrogen atom, and Z B4 GA=CR B7 - is preferred, and Z B1 and Z B3 is a nitrogen atom, and Z B2 and Z B4 GA=CR B7 - is a more preferred embodiment. Above R B7 is preferably a hydrogen atom or a monovalent organic group. Also, Z B1 , Z B2 and Z B3 is a nitrogen atom, and Z B4 GA=CR B7 -If R B7 is preferably a binding site to another structure. R B7A preferred embodiment of the monovalent organic group in B1 The preferred embodiments are the same as those of the monovalent organic group in the above.

[0153] R contained in formula (B-1) B1 and R B7 At least one of these represents a binding site with other structures, and at least R B1 In formula (B-1), R preferably represents a bonding site with another structure. B1 Only represents the binding site with other structures, and R B7 and each independently represent a hydrogen atom or a monovalent organic group is also one of the preferred embodiments of the present invention.

[0154] In formula (B-2), Z B5 and Z B6 are each independently, =CR B8 - or a nitrogen atom. Among them, Z B5 and Z B6 each represents a nitrogen atom, or Z B5 is the nitrogen atom, Z B6 GA=CR B8 - are preferred. In formula (B-2), Z B5 and Z B6 When both represent nitrogen atoms, R B6 In formula (B-2), Z preferably represents a bonding site with another structure. B5 and Z B6 each represents a nitrogen atom, and R B6 An embodiment in which only represents a binding site to another structure is also one of the preferred embodiments of the present invention. In formula (B-2), Z B5 is the nitrogen atom, Z B6 GA=CR B8 -, respectively, R B8 In formula (B-2), Z preferably represents a bonding site with another structure. B5 is the nitrogen atom, Z B6 GA=CR B8 -, and R B8An embodiment in which only represents a binding site to another structure is also one of the preferred embodiments of the present invention.

[0155] In formula (B-2), R B2 ~R B5 Preferably, each independently represents a hydrogen atom or a monovalent organic group. B2 ~R B5 A preferred embodiment of the monovalent organic group in B1 The preferred embodiments are the same as those of the monovalent organic group in the above. In formula (B-2), Z B5 is the nitrogen atom, Z B6 GA=CR B8 -, respectively, R B6 R preferably represents a hydrogen atom or a monovalent organic group. B6 A preferred embodiment of the monovalent organic group in B1 The preferred embodiments are the same as those of the monovalent organic group in the above. In other cases, R B6 It is preferable that Z represents a binding site with another structure. B5 is the nitrogen atom, Z B6 GA=CR B8 -, respectively, R B8 Preferably, represents a binding site to another structure. In formula (B-2), R B8 preferably represents a binding site to another structure. Z B5 and Z B6 Both are =CR B8 -, one R B8 It is preferred that R represents a bonding site with another structure, and the other represents a hydrogen atom or a monovalent organic group. B8 A preferred embodiment of the monovalent organic group in B1 The preferred embodiments are the same as those of the monovalent organic group in the above.

[0156] R included in formula (B-2) B2 ~R B6 and R B8 At least one of these represents a binding site with other structures, and at least R B6 or RB8 In formula (B-2), R preferably represents a bonding site with another structure. B6 and R B8 Only one of these represents the binding site with the other structure, and R B6 and R B8 the other of the two and R B2 ~R B5 and each independently represent a hydrogen atom or a monovalent organic group is also one of the preferred embodiments of the present invention.

[0157] Among these, the azole group is preferably a group represented by any one of the following formulae (B-3) to (B-6). [ka]

[0158] In formulas (B-3) to (B-6), R B9 ~R B20 each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to another structure. In formulas (B-3) to (B-6), R B9 ~R B20 is preferably a hydrocarbon group, an amino group, or a nitro group. In formulas (B-3) to (B-6), R B9 ~R B20 Preferred embodiments of the hydrocarbon group in the above R B1 The preferred embodiments are the same as those of the hydrocarbon group in the above. Also, R B9 ~R B20 The amino group in may be a substituted amino group or an unsubstituted amino group.

[0159] [Other silane coupling agents] Furthermore, compound B may be a compound (another silane coupling agent) that does not have a photodimerization reactive group or an azole group but has an alkoxysilyl group. Examples of other silane coupling agents, for example, compounds described in paragraph 0167 of WO 2015 / 199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011 / 080992, compounds described in paragraphs 0060 to 0061 of JP 2014-191252, compounds described in paragraphs 0045 to 0052 of JP 2014-041264, compounds described in paragraph 0055 of WO 2014 / 097594, compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent: In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0160] [ka]

[0161] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of suitable silanes include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more.

[0162] Compound B may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular compound B"), or may be a resin (hereinafter also referred to as "resin B"). In addition, from the viewpoint of adhesion of the cured product to metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound B and the resin B. From the viewpoint of adhesion, compound B is preferably a resin.

[0163] [Low molecular compound B] The molecular weight of the low-molecular-weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0164] The number of photodimerizable groups in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of alkoxysilyl groups in the low molecular weight compound B is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0165] The low molecular weight compound B is preferably a compound represented by the above formula (B1-1) or (B1-2), and may also be any of the other silane coupling agents described above.

[0166] [Resin B] The weight average molecular weight of Resin B is preferably from 2,000 to 100,000, more preferably from 3,000 to 70,000, and even more preferably from 5,000 to 50,000.

[0167] The molar amount of photodimerization reactive groups in 1 g of Resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0168] The molar amount of the polymerizable group in 1 g of Resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0169] The molar amount of alkoxysilyl groups in 1 g of Resin B is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0170] Resin B is preferably a resin having a repeating unit containing a photodimerization group, a repeating unit containing a radically polymerizable group, and a repeating unit containing an alkoxysilyl group, and more preferably a resin having a repeating unit containing a photodimerization group and a repeating unit containing an alkoxysilyl group. Resin B may contain one type of each of these repeating units alone, or may contain two or more types.

[0171] -Repeating unit containing a photodimerization group- Resin B preferably contains a repeating unit represented by the following formula (BL-1) as a repeating unit containing a photodimerization reactive group. [ka] In formula (BL-1), L L1 represents a single bond or a divalent linking group, and X L1 represents a photodimerization reactive group, and R represents a hydrogen atom or a methyl group. In formula (BL-1), L L1 represents a single bond or a divalent linking group, and a divalent linking group is preferred. The divalent linking group is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Among these, L L1 is preferably a group represented by the following formula (BL-1-1). [ka] In formula (BL-1-1), L L4 represents a divalent linking group, LL5 represents a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (BL-1), A L1 and A L2 -O- or -NR N -, and # represents X in (BL-1). L1 represents the binding site with R N is as described above.

[0172] In formula (BL-1-1), L L4 represents a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0173] In formula (BL-1-1), L L5 is preferably a single bond. L5 In the case where is a divalent linking group, a preferred embodiment is the above-mentioned L L4 This is the same as the preferred embodiment of the above.

[0174] In formula (BL-1-1), A L1 and A L2 -O- or -NR N -, and is preferably -O-. Above R N is as described above.

[0175] In formula (BL-1), X L1 The preferred embodiments of are the same as the preferred embodiments of the photodimerization reactive group in compound B described above.

[0176] -Repeating unit containing a radically polymerizable group- Resin B preferably contains a repeating unit represented by the following formula (BP-1) as a repeating unit containing a radically polymerizable group. [ka] In formula (BP-1), A P -O- or -NR N - represents L P represents an (n+1)-valent linking group, and X P represents a radical polymerizable group, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

[0177] In formula (BP-1), A P -O- or -NR N -, with -O- being preferred. N is as described above.

[0178] In formula (BP-1), L P represents an (n+1)-valent linking group, and is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0179] In formula (BP-1), X P The preferred embodiments of are the same as the preferred embodiments of the radical polymerizable group in compound B described above.

[0180] In formula (BP-1), n ​​represents an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 1.

[0181] -Repeating unit containing an alkoxysilyl group- Resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing an alkoxysilyl group. [ka] In formula (BA-2), A 3 -O- or -NR N - represents L P1 represents a divalent linking group, and X P1 represents an alkoxysilyl group, and R represents a hydrogen atom or a methyl group.

[0182] In formula (BA-2), A 3 -O- or -NR N -, with -O- being preferred. N is as described above.

[0183] In formula (BA-2), L P1 represents a divalent linking group, and is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0184] In formula (BA-2), X P1 The preferred embodiments of are the same as the preferred embodiments of the alkoxysilyl group in compound B described above.

[0185] -Repeating unit containing an azole group- Resin B also preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group. [ka] In formula (BA-1), L 3 represents a single bond or a divalent linking group, and X 3 represents an azole group, and R represents a hydrogen atom or a methyl group. In formula (BA-1), L 3 represents a single bond or a divalent linking group. The divalent linking group is a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Among these, L 3 is preferably a single bond, a group represented by the following formula (BA-1-1) or a group represented by the following formula (BA-1-2). [ka] In formula (BA-1-1) or formula (BA-1-2), L 4 represents a divalent linking group, L 5 represents a single bond or a divalent linking group, L 6 represents a divalent linking group, L 7 represents a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (BA-1), A 1 and A 2 -O- or -NR N -, and # represents X in (BA-1). 3 represents the binding site with

[0186] In formula (BA-1-1), L 4 represents a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR NA group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred. Above R N is as described above. The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably an alkylene group. The hydrocarbon group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

[0187] In formula (BA-1-1), L 5 is preferably a single bond. 5 When L is a divalent linking group, 5 represents a hydrocarbon group, or a hydrocarbon group and -O-, -S-, -C(=O)-, -S(=O)2-, or -NR N A group represented by a bond to at least one group selected from the group consisting of - is preferred, and a hydrocarbon group is more preferred.

[0188] In formula (BA-1-2), L 6 is L in formula (BA-1-1) 4 The same applies to the preferred embodiments.

[0189] In formula (BA-1-2), L 7 is preferably a divalent linking group. 7 When L is a divalent linking group, 7 A preferred embodiment of the formula (BA-1-1) is L 5 is the same as the preferred embodiment when is a divalent linking group.

[0190] In formula (BA-1-1) or formula (BA-1-2), A 1 and A 2 -O- or -NR N -, with -O- being preferred. N is as described above.

[0191] In formula (BA-1), X 3The preferred embodiment of the azole group in formula (BA-1) is as described above. 3 This corresponds to the binding site for

[0192] Resin B may contain only one type of repeating unit represented by formula (BA-1), or may contain two or more types. When Resin B contains a repeating unit containing an azole group, the molar amount of the azole group contained in 1 g of Resin B is preferably 0.001 to 5 mmol / g, and more preferably 0.01 to 1 mmol / g.

[0193] -Other repeating units- Resin B may further have a repeating unit other than the repeating unit represented by formula (BL-1), formula (BP-1), formula (BA-2) or formula (BA-1).

[0194] [Specific example] Specific examples of compound B include, but are not limited to, the compounds used in the examples.

[0195] [Content] The content of compound B is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of compound B, or may contain two or more types of compound B. When two or more types of compound B are contained, the total amount is preferably within the above range.

[0196] <Compound C Having an Azole Group and at Least One Group Selected from the Group Consisting of a Radical Polymerizable Group and a Photodimerization Reactive Group> The photosensitive resin composition of the present invention preferably further contains a compound C having an azole group and at least one group selected from the group consisting of a radically polymerizable group and a photodimerization reactive group. Compound C is a compound that does not contain an alkoxysilyl group. The compounds that fall under the above-mentioned specific resin or compound B are not considered to fall under compound C.

[0197] The azole group, radical polymerizable group, and photodimerizable group in compound C are the same as the azole group, radical polymerizable group, and photodimerizable group in compound B, respectively, and preferred embodiments are also the same.

[0198] Compound C may be a compound having a molecular weight of less than 2,000 (hereinafter also referred to as "low molecular compound C"), or may be a resin (hereinafter also referred to as "resin C"). In addition, from the viewpoint of adhesion of the cured product to metal, it is also preferable that the photosensitive resin composition contains both the low molecular weight compound C and the resin C. From the viewpoint of adhesion, the compound C is preferably a resin.

[0199] [Low molecular compound C] The molecular weight of the low-molecular-weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.

[0200] The number of azole groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of photodimerizable groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1. The number of radically polymerizable groups in the low molecular weight compound C is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.

[0201] [Resin C] The weight average molecular weight of Resin C is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000.

[0202] The molar amount of azole groups in 1 g of Resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0203] The molar amount of photodimerization reactive groups in 1 g of resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0204] The molar amount of the radically polymerizable group in 1 g of Resin C is preferably 0.001 to 1 mmol / g, more preferably 0.002 to 0.3 mmol / g, and even more preferably 0.005 to 0.1 mmol / g.

[0205] Resin C is preferably a resin having a repeating unit having an azole group, and at least one repeating unit selected from the group consisting of a repeating unit containing a photodimerization group and a repeating unit containing a radically polymerizable group, and more preferably a resin having a repeating unit having an azole group and a repeating unit containing a photodimerization group. Resin C may contain one kind of each of these repeating units alone, or may contain two or more kinds. Preferred embodiments of these repeating units are the same as those of the repeating units in Resin B. Resin C may further include other repeating units.

[0206] [Specific example] Specific examples of compound C include, but are not limited to, the compounds used in the examples.

[0207] [Content] The content of compound C is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of compound C, or may contain two or more types of compound C. When two or more types of compound C are contained, the total amount is preferably in the above range.

[0208] <Compound D having an azole group but not having an alkoxysilyl group, a radical polymerizable group, or a photodimerization reactive group> From the viewpoint of adhesion of the obtained cured product to metal, the photosensitive resin composition of the present invention preferably contains a compound D that has an azole group but does not have an alkoxysilyl group, a radically polymerizable group, or a photodimerization reactive group.

[0209] Compound D is preferably a compound represented by the following formula (D1-1) or (D1-2). [ka] In formula (D1-1), Z 1 ~Z 4 are each independently, =CR 7 - or a nitrogen atom, R 1 represents a hydrogen atom or a monovalent organic group, and R 7 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-1) does not contain an alkoxysilyl group, a radically polymerizable group, or a photodimerizable group; In formula (D1-2), Z 5 ~Z 6 are each independently, =CR 8 - or a nitrogen atom, R 2 ~R 6 each independently represents a hydrogen atom or a monovalent organic group, R 8 represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (D1-2) does not include an alkoxysilyl group, a radically polymerizable group, or a photodimerizable group.

[0210] In formula (D1-1), Z 1 ~Z 4 are each independently, =CR 7 - or a nitrogen atom. Among them, Z 1 ~Z 4 One of them is a nitrogen atom and three are =CR 7 -Z 1 ~Z 4 Two of them are nitrogen atoms and two are =CR 7 -, or Z 1 ~Z 4 Three of them are nitrogen atoms and one is =CR 7 - is preferred. Among these, Z 1 and Z 3 is a nitrogen atom, and Z 2 and Z 4 GA=CR 7 -Z 1 and Z 2 is a nitrogen atom, and Z 3 and Z 4 GA=CR 7 -, or Z 1 , Z 2 and Z 3 is a nitrogen atom, and Z 4 GA=CR 7 - is preferred, and Z 1 and Z 3 is a nitrogen atom, and Z 2 and Z 4 GA=CR B7 -, or Z 1 , Z 2 and Z 3 is a nitrogen atom, and Z 4 GA=CR 7 - is a more preferred embodiment.

[0211] In formula (D1-1), R 1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The hydrocarbon group or alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0212] In formula (D1-1), R 7 A preferred embodiment of R 1 is the same as:

[0213] In formula (D1-2), Z 5 and Z 6 are each independently, =CR 8 - or a nitrogen atom. Among them, Z 5 and Z 6 each represents a nitrogen atom, or Z 5 is the nitrogen atom, Z 6 GA=CR 8 - are preferred.

[0214] In formula (D1-2), R 2 ~R 6 , R 8 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0215] [Specific example] Specific examples of Compound D include, but are not limited to, the compounds used in the Examples.

[0216] [Content] The content of compound D is preferably 0.05 to 10 mass %, more preferably 0.10 to 5 mass %, and even more preferably 0.15 to 2 mass %, based on the total solid content of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one type of compound D, or may contain two or more types of compound D. When two or more types of compound D are contained, the total amount is preferably in the above range.

[0217] <Solvent> The 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, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0218] Examples of 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 alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionates, Preferred examples of the alkyl cypropionate include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0219] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0220] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0221] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0222] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0223] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0224] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0225] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0226] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0227] In the present invention, preferred are solvents selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or mixed solvents composed of two or more of these solvents. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0228] From the viewpoint of coatability, the content of the solvent is preferably an amount that makes the total solids concentration of the resin composition of the present invention 5 to 80 mass %, more preferably an amount that makes it 5 to 75 mass %, even more preferably an amount that makes it 10 to 70 mass %, and even more preferably an amount that makes it 20 to 70 mass %. The content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method.

[0229] The resin composition of the present invention may contain only one solvent or two or more solvents. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0230] [Photopolymerization initiator] The composition of the present invention includes a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts in some way with a photoexcited sensitizer to generate active radicals.

[0231] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L·mol -1 ·cm -1 Preferably, the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0232] Any known photoradical polymerization initiator can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol.19, No.3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A are mentioned, the contents of which are also incorporated herein.

[0233] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0234] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0235] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF).

[0236] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF).

[0237] As the aminoacetophenone initiator, compounds described in JP-A-2009-191179, whose maximum absorption wavelength matches a wavelength light source such as 365 nm or 405 nm, can also be used, the contents of which are incorporated herein by reference.

[0238] Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Also usable are Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF).

[0239] Examples of metallocene compounds include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

[0240] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0241] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232) compounds described in, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like, the contents of which are incorporated herein by reference.

[0242] Preferred oxime compounds include, for example, compounds having the following structure, as well as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group of >C=NOC(=O)- within the molecule.

[0243] [ka]

[0244] Commercially available products such as IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitable. TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Oxime compounds having the following structure can also be used. [ka]

[0245] As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP 2014-137466 A and Japanese Patent No. 06636081 A, the contents of which are incorporated herein by reference.

[0246] As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in WO 2013 / 083505, the contents of which are incorporated herein by reference.

[0247] It is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and compound (C-3) described in paragraph 0101 of JP 2013-164471 A, the contents of which are incorporated herein by reference.

[0248] As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, the contents of which are incorporated herein by reference. Another example of the oxime compound having a nitro group is ADEKA ARCLES NCI-831 (manufactured by ADEKA Corporation).

[0249] The photoradical polymerization initiator may also be an oxime compound having a benzofuran skeleton, specific examples of which include OE-01 to OE-75 described in WO 2015 / 036910.

[0250] As the photoradical polymerization initiator, an oxime compound having a hydroxyl group-containing substituent bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in WO 2019 / 088055, the contents of which are incorporated herein by reference.

[0251] As a photopolymerization initiator, an aromatic ring group Ar in which an electron-withdrawing group is introduced into the aromatic ring is used. OX1 It is also possible to use an oxime compound having the aromatic ring group Ar OX1Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred, and an acyl group is more preferred because it is easier to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group. An alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group is more preferred, and an alkoxy group, an alkylsulfanyl group, or an amino group is even more preferred.

[0252] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, RX3 ~R X14 each independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of the groups is an electron-withdrawing group.

[0253] In the above formula, R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 , R X14 is preferably a hydrogen atom.

[0254] Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

[0255] Most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents of which are incorporated herein by reference.

[0256] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0257] More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, and at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and it is even more preferred to use a metallocene compound or an oxime compound.

[0258] In addition, the photoradical polymerization initiator may be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-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 fused with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzil dimethyl ketal, etc. Compounds represented by the following formula (I) may also be used.

[0259] [ka]

[0260] In formula (I), R I00is 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 a phenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R I01 is a group represented by formula (II), or R I00 is the same group as R I02 ~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 atom.

[0261] [ka]

[0262] In the formula, R I05 ~R I07 is R in the above formula (I). I02 ~R I04 is the same as

[0263] Furthermore, the photoradical polymerization initiator may also be the compounds described in paragraphs 0048 to 0055 of WO 2015 / 125469, the contents of which are incorporated herein by reference.

[0264] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, WO-A-2015 / 004565, WO-A-2016-532675, paragraphs 0407 to 0412, and WO-A-2017 / 033680, paragraphs 0039 to 0055; compounds (E) and (G) described in JP-A-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Application Publication No. 34963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0265] When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0266] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isodiethylaminobenzoate amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, and the like. Other sensitizing dyes may also be used. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0267] When the resin composition 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 %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0268] [Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0269] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0270] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total amount thereof is preferably within the above range.

[0271] [Photoacid generator] The resin composition of the present invention preferably contains a photoacid generator. The photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light of 200 nm to 900 nm. The light to be irradiated preferably has a wavelength of 300 nm to 450 nm, more preferably 330 nm to 420 nm. The photoacid generator, whether used alone or in combination with a sensitizer, is preferably a photoacid generator that can generate an acid upon exposure to light. Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric monoesters, phosphoric diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

[0272] Examples of the photoacid generator used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salt compounds. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.

[0273] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and / or sulfonamide-bonded to a polyhydroxy polyamino compound. While not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinone diazide, it is preferable that, on average, 40 mol% or more of the total functional groups are substituted with quinone diazide. By incorporating such quinone diazide compounds, a resin composition can be obtained that is sensitive to common ultraviolet rays, such as the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp.

[0274] Specific examples of hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisO CP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, T riML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industries), BIR-OC, BI P-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (product names, Examples of suitable phenolic resins include, but are not limited to, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and novolak resins.

[0275] Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0276] Specific examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0277] Among these, it is preferable that the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group, which can provide higher sensitivity to i-line exposure and higher resolution.

[0278] The content of the quinone diazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. By setting the content of the quinone diazide compound within this range, a contrast between exposed and unexposed areas can be obtained, thereby achieving higher sensitivity, which is preferable. Furthermore, a sensitizer or the like may be added as necessary.

[0279] The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter also simply referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), or the formula (OS-103), formula (OS-104), or formula (OS-105) described below.

[0280] [ka]

[0281] In formula (OS-1), X 3 represents an alkyl group, an alkoxy group, or a halogen atom. 3 When there are a plurality of X's, they may be the same or different. 3 The alkyl group and alkoxy group in the above X may have a substituent.3 The alkyl group in X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. 3 The alkoxy group in the above X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 The halogen atom in is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

[0282] In formula (OS-1), m3 is 3, and X 3 is a methyl group, and X 3 The substitution position of is the ortho position, and R 34 Particularly preferred are compounds in which is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group.

[0283] Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A No. 2011-209692 and paragraphs 0158 to 0167 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference.

[0284] [ka]

[0285] In formula (OS-103) ~ formula (OS-105), R s1 represents an alkyl group, an aryl group, or a heteroaryl group, and R may be present in plural. s2 R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and there may be more than one R s6 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; Xs represents O or S; ns represents 1 or 2; and ms represents an integer of 0 to 6. In formula (OS-103) ~ formula (OS-105), R s1 The alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by the formula (I) may have a known substituent as long as the effects of the present invention are achieved.

[0286] In formula (OS-103) ~ formula (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. s2 Among R, it is preferred that one or two of them are an alkyl group, an aryl group, or a halogen atom, more preferably that one of them is an alkyl group, an aryl group, or a halogen atom, and particularly preferably that one of them is an alkyl group and the remaining are hydrogen atoms. s2 The alkyl group or aryl group represented by the formula (I) may have a known substituent within the range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104), or formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5- or 6-membered ring.

[0287] In formulae (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2. In formula (OS-103) ~ formula (OS-105), R s6 The alkyl group (preferably having 1 to 30 carbon atoms) and alkyloxy group (preferably having 1 to 30 carbon atoms) represented by the following formula may have a substituent. In formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0288] Furthermore, the compound represented by formula (OS-103) above is particularly preferably a compound represented by formula (OS-106), formula (OS-110), or formula (OS-111) below; the compound represented by formula (OS-104) above is particularly preferably a compound represented by formula (OS-107) below; and the compound represented by formula (OS-105) above is particularly preferably a compound represented by formula (OS-108) or formula (OS-109) below. [ka]

[0289] In formula (OS-106) ~ formula (OS-111), R t1 represents an alkyl group, an aryl group, or a heteroaryl group; R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and R t2 represents a hydrogen atom or a methyl group. In formula (OS-106) ~ formula (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

[0290] In formula (OS-106) ~ formula (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0291] In formula (OS-106) ~ formula (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom. R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In the oxime sulfonate compound, the steric structure of the oxime (E, Z) may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP 2011-209692 A and paragraphs 0168 to 0194 of JP 2015-194674 A, the contents of which are incorporated herein by reference.

[0292] Other preferred embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

[0293] [ka]

[0294] In formula (OS-101) or formula (OS-102), R u9represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. u9 is more preferably a cyano group or an aryl group, and R u9 is more preferably a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH-, -NR u5 -, -CH2-, -CR u6 H- or CR u6 R u7 - represents R u5 ~R u7 each independently represents an alkyl group or an aryl group.

[0295] In formula (OS-101) or formula (OS-102), R u1 ~R u4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, or an aryl group. u1 ~R u4 Two of the rings may be bonded to each other to form a ring. In this case, the rings may be condensed together with the benzene ring to form a condensed ring. u1 ~R u4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and R u1 ~R u4 It is also preferable that at least two of R are bonded to each other to form an aryl group. u1 ~R u4 is preferably a hydrogen atom. Each of the above-mentioned substituents may further have a substituent.

[0296] The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195 to 0207 of JP-A No. 2015-194674, the contents of which are incorporated herein by reference. Among the above compounds, the following compounds b-9, b-16, b-31, and b-33 are preferred. [ka] Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and MBZ-101 (manufactured by Midori Chemical Industries, Ltd.).

[0297] Further, compounds represented by the following structural formulas are also preferred examples. [ka]

[0298] Specific examples of the organic halogenated compounds include those described in Wakabayashi et al., Bull Chem. Soc. Japan, vol. 42, p. 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-4605 / 1971, JP-A-48-36281 / 1973, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and M.P. Hutt, Journal of Heterocyclic Chemistry, Vol. 1 (No. 3), (1970), the contents of which are incorporated herein by reference. In particular, preferred examples include oxazole compounds substituted with a trihalomethyl group and S-triazine compounds. More preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, Azine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine] phenyl)-2,4-butadienyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-nathoxynaphthyl)-4,6- Examples thereof include bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

[0299] Examples of organic borate compounds include those described in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, and Kunz, Martin, "Rad Tech '98, Proceedings of April 19-22, 1998, Chicago, etc.; organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561; organic boron iodine complexes described in JP-A-6-175554 and JP-A-6-175553; Specific examples include organoboron transition metal coordination complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, and the like, the contents of which are incorporated herein by reference.

[0300] Examples of disulfone compounds include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318, and diazodisulfone compounds.

[0301] Examples of the onium salt compounds include diazonium salts described in I S Schlesinger, Photogr. Sci. Eng., 18, 387 (1974) and T S Bal et al., Polymer, 21, 423 (1980); ammonium salts described in U.S. Pat. No. 4,069,055 and JP-A-4-365049; phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056; iodine salts described in European Patent Nos. 104, 143, U.S. Pat. Nos. 339,049 and 410,201, and JP-A-2-150848 and JP-A-2-296514. sulfonium salts described in European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, and German Patent Nos. 2,904,626, 3,604,580, and 3,604,581; Examples of suitable onium salts include the selenonium salts described in J.V. Crivello et al., Macromolecules, 10(6), 1307 (1977) and J.V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), the arsonium salts described in C.S. Wen et al., Teh., Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, October (1988), and onium salts such as pyridinium salts, the contents of which are incorporated herein by reference.

[0302] Examples of the onium salt include onium salts represented by the following general formulae (RI-I) to (RI-III). [ka] In formula (RI-I), Ar 11represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms in the alkyl group or an arylamide group having 6 to 20 carbon atoms in the aryl group, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. 11 - represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the viewpoint of stability, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, or a sulfinate ion is preferred. 21 , Ar 22 each independently represents an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group each independently has 1 to 12 carbon atoms, an alkylamido group or arylamido group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. -represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the viewpoints of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred. 31 , R 32 , R 33 each independently represents an aryl group, alkyl group, alkenyl group, or alkynyl group having 6 to 20 carbon atoms, each of which may have 1 to 6 substituents, and is preferably an aryl group from the viewpoints of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group carbon atoms each independently have 1 to 12 carbon atoms, an alkylamido group or arylamido group in which the alkyl group carbon atoms have 1 to 12 carbon atoms, a carbonyl group, a carboxy group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 31 - represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfonate ion, or a sulfate ion, and from the standpoint of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

[0303] Specific examples of preferred photoacid generators include the following: [ka] [ka] [ka] [ka]

[0304] The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, even more preferably 0.5 to 10 mass %, still more preferably 0.5 to 3 mass %, and even more preferably 0.5 to 1.2 mass %, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination of two or more. In the case of a combination of two or more, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination to impart photosensitivity to a desired light source.

[0305] <Thermal acid generator> The compositions of the present invention may also include a thermal acid generator. The thermal acid generator generates an acid upon heating and has the effect of promoting the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

[0306] The thermal decomposition starting temperature of the thermal acid generator is preferably 50° C. to 270° C., more preferably 50° C. to 250° C. In addition, it is preferable to select a thermal acid generator that does not generate acid during drying (pre-baking: about 70 to 140° C.) after the composition is applied to a substrate, but generates acid during final heating (curing: about 100 to 400° C.) after patterning by subsequent exposure and development, because this can suppress a decrease in sensitivity during development. The thermal decomposition starting temperature is determined as the lowest exothermic peak temperature when the thermal acid generator is heated to 500°C at 5°C / min in a pressure-resistant capsule. An example of an instrument used to measure the thermal decomposition onset temperature is Q2000 (manufactured by TA Instruments).

[0307] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or a haloalkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of JP 2013-072935 A.

[0308] Among these, those which generate alkylsulfonic acids having 1 to 4 carbon atoms or haloalkylsulfonic acids having 1 to 4 carbon atoms are more preferred from the viewpoint of remaining less in the organic film and not deteriorating the physical properties of the organic film, and examples thereof include (4-hydroxyphenyl)dimethylsulfonium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium methanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium methanesulfonate, and (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate. Preferred thermal acid generators include benzophenone, (4-((methoxycarbonyl)oxy)phenyl)dimethylsulfonium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylsulfonium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)sulfonium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propanenitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

[0309] Furthermore, the compounds described in paragraph 0059 of JP-A No. 2013-167742 are also preferred as thermal acid generators.

[0310] The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the specific resin. By including 0.01 parts by mass or more, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic film. Furthermore, from the viewpoint of the electrical insulation properties of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0311] <Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator according to the present invention is not particularly limited, and known base generators can be used. Examples of known base generators that can be used include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), and formula (B3). [ka]

[0312] In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb 1 and Rb 2 cannot be hydrogen atoms at the same time. 1 , Rb 2 and Rb 3 None of these has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply to cases in which the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, a case in which the bonded carbon atom forms an amide group together with the nitrogen atom.

[0313] In formulas (B1) and (B2), Rb 1 , Rb 2 and Rb 3 Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0314] More specifically, Rb 1 and Rb 2is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. 1 and Rb 2 is particularly preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0315] Rb 3Examples of the group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. 3 may further have a substituent within the range in which the effects of the present invention are exhibited.

[0316] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2). [ka]

[0317] In the formula, Rb 11 and Rb 12 , and Rb 31 and Rb 32 respectively represent Rb in formula (B1). 1 and Rb 2 is the same as Rb 13is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and may have a substituent within the range in which the effects of the present invention are exhibited. 13 is preferably an arylalkyl group.

[0318] Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0319] Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and still more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 12 carbon atoms), and an aryl group is preferred.

[0320] The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [ka]

[0321] Rb 11 and Rb 12is Rb in formula (B1-1) 11 and Rb 12 is synonymous with. Rb 15 and Rb 16 represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0322] [ka]

[0323] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. N1 and R N2 each independently represents a monovalent organic group.

[0324] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms to be linked in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4. [ka]

[0325] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0326] The base generator also preferably contains a compound represented by the following formula (N1). [ka]

[0327] In formula (N1), R N1 and R N2 each independently represents a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0328] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0329] In formula (N1), R N1 and R N2 R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. N1 and R N2 When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0330] R N1 and R N2Examples of the aliphatic hydrocarbon group constituting the formula (I) include a linear or branched chain alkyl group, a cyclic alkyl group, a group formed by combining a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The group representing the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group representing the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. Among these, from the viewpoint of increasing the boiling point of the decomposition product base described later, R N1 and R N2 is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0331] R N1 and R N2may be linked to each other to form a cyclic structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. N1 and R N2 The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring, and is preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, or a morpholine ring.

[0332] R C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

[0333] The protecting group is preferably a protecting group that is decomposed by the action of an acid or a base, and a protecting group that is decomposed by an acid is preferred.

[0334] Specific examples of the protecting group include linear or cyclic alkyl groups, and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specific examples include a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0335] The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group which may have an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group is more preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is even more preferred. It is preferable that these groups do not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group (e.g., an arylene alkyl group) formed by combining a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

[0336] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a linear alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0337] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 or 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

[0338] Examples of the base generator include the following, but the present invention is not limited thereto.

[0339] [ka]

[0340] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0341] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0342] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [ka]

[0343] Specific examples of iminium salts include the following compounds, but the present invention is not limited to these. [ka]

[0344] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0345] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[0346] [Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0347] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. In addition, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0348] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0349] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. For specific examples, see paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0350] Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, and many other compounds. Examples of suitable compounds include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the resulting compound, urethane (meth)acrylates as described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates as described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, and polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also suitable. Further examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

[0351] In addition, as preferred radical crosslinking agents other than those described above, compounds having a fluorene ring and two or more groups having an ethylenically unsaturated bond, as described in JP-A No. 2010-160418, JP-A No. 2010-129825, Japanese Patent No. 4364216, etc., and cardo resins can also be used.

[0352] Other examples include the specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and the vinylphosphonic acid compounds described in Japanese Patent Laid-Open No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Laid-Open No. 61-022048 can also be used. Furthermore, compounds introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Adhesion Association, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0353] In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of WO 2015 / 199219 A can also be preferably used, the contents of which are incorporated herein by reference.

[0354] In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) together with specific examples thereof, can also be used as radical crosslinking agents.

[0355] Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

[0356] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), as well as compounds in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

[0357] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer Corporation; SR-209, 231, and 239, difunctional methacrylates having four ethyleneoxy chains, manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.; and urethane Examples of such oligomers include Oligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0358] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A No. 63-277653, JP-A No. 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0359] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0360] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0361] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain. In the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product). Examples of the monofunctional radical crosslinking agent include (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-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher at normal pressure are also preferred as the monofunctional radical crosslinking agent. Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0362] When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0363] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0364] [Other crosslinking agents] The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred. Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used.In addition, oligomers formed by self-condensation of the methylol groups of these compounds may also be used. As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

[0365] Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine. The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups contained in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.

[0366] [ka]

[0367] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represents a monovalent organic group, and may be bonded to each other to form a ring.

[0368] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

[0369] [ka]

[0370] In the formula, X represents a single bond or a divalent organic group, and each R 104 each independently represents an alkyl group or an acyl group, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes under the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, -C(R4 )2COOR 5 A group represented by (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is eliminated by the action of an acid. R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. A group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated under the action of an acid, -C(R 4 )2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be either linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents within the range in which the effects of the present invention can be obtained.

[0371] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0372] The group that decomposes under the action of an acid to generate an alkali-soluble group or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

[0373] Specific examples of compounds having an alkoxymethyl group include the following structures: Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds is replaced with an acyloxymethyl group: Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds:

[0374] [ka]

[0375] [ka]

[0376] The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be commercially available or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.

[0377] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0378] Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; ethyleneurea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea; propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; Examples include 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0379] Specific examples of benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0380] In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], and 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol.

[0381] As other crosslinking agents, commercially available products may be used, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0382] The resin composition of the present invention also preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0383] -Epoxy compounds (compounds containing epoxy groups)- The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200°C or less, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of an epoxy compound is effective in low-temperature curing of the resin composition of the present invention and suppressing warpage.

[0384] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the elastic modulus and suppresses warpage. The polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0385] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark) BEO-20E, Likaresin (registered trademark) BEO-60E, Likaresin (registered trademark) HBE-100, Likaresin (registered trademark) DME-100, Likaresin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S , EP-3950S (all trade names, manufactured by ADEKA Corporation), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000 EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like. The following compounds are also preferably used.

[0386] [ka]

[0387] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0388] Among the above structures, n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0389] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, such as 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples that can be suitably used include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., and these may be used alone or in combination of two or more.

[0390] -Benzoxazine compounds (compounds having a benzoxazolyl group)- Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that no degassing occurs during curing, and furthermore, they reduce thermal shrinkage and suppress the occurrence of warping.

[0391] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds, which may be used alone or in combination of two or more.

[0392] The content of the other crosslinking agent is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, even more preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %, based on the total solid content of the resin composition of the present invention. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total content thereof is preferably within the above range.

[0393] <Metal adhesion improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0394] [Aluminum-based adhesion promoter] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0395] In addition, other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935, the contents of which are incorporated herein by reference.

[0396] The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By ensuring that the content is equal to or greater than the lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be one type, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0397] <Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

[0398] Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, 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-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbonate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. Additionally, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015 / 125469 A can also be used, the contents of which are incorporated herein by reference.

[0399] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition of the present invention.

[0400] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0401] <Acid scavenger> The resin composition of the present invention preferably contains an acid scavenger to reduce performance changes over time from exposure to heating. Here, the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa. As the acid scavenger, a compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, and primary amines, secondary amines, tertiary amines, and ammonium salts are preferred, with secondary amines, tertiary amines, and ammonium salts being more preferred. Preferred examples of the acid scavenger include compounds having an imidazole structure, a diazabicyclo structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and aniline derivatives having a hydroxyl group and / or an ether bond. When the acid scavenger has an onium structure, it is preferably a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.

[0402] Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N,N-bis(hydroxyethyl)aniline.

[0403] Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, diphenyl ... diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine, diphenylamine ethylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylmorpholine, and the like.

[0404] These acid scavengers may be used alone or in combination of two or more. The composition according to the present invention may or may not contain an acid scavenger. When the composition contains an acid scavenger, the content of the acid scavenger is usually 0.001 to 10 mass %, and preferably 0.01 to 5 mass %, based on the total solid content of the composition.

[0405] The ratio of the acid generator to the acid scavenger used is preferably acid generator / acid scavenger (molar ratio) = 2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing a decrease in resolution due to thickening of the relief pattern over time after exposure until heat treatment, the molar ratio is preferably 300 or less. The acid generator / acid scavenger (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0406] <Other additives> The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organotitanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, provided that the effects of the present invention are achieved. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0407] [Surfactant] As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0408] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

[0409] Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, and FC4432 (all manufactured by 3M Corporation). Examples of suitable surfactants include Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.), and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). The fluorine-based surfactants may also be compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant, and specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference. As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention. [ka]

[0410] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. The fluorine-containing surfactant may be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0411] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0412] Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie Co., Ltd.).

[0413] Examples of hydrocarbon surfactants include Paionin A-76, Newkalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, and Paionin P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

[0414] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0415] Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0416] Specific examples of anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

[0417] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0418] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during the drying process after application.

[0419] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference.

[0420] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content thereof is preferably within the above range.

[0421] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Adding a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0422] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0423] When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass %, and even more preferably 0.5 to 15 mass %. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0424] [Inorganic particles] The resin composition of the present invention may contain inorganic particles, such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0425] The average particle size of the inorganic particles is preferably from 0.01 to 2.0 μm, more preferably from 0.02 to 1.5 μm, even more preferably from 0.03 to 1.0 μm, and particularly preferably from 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurements are difficult, centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method can also be used.

[0426] [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber, such as a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and pt-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-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber 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-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

[0427] Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of the triazine-based ultraviolet absorber include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

[0428] In the present invention, the above-mentioned various ultraviolet absorbents may be used singly or in combination of two or more. The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid mass of the composition of the present invention.

[0429] [Organotitanium Compounds] The resin composition of the present embodiment may contain an organotitanium compound. When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0430] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide resin compositions with good storage stability and produce good curing patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisop...

Claims

1. At least one resin selected from the group consisting of polyimide and polyamideimide; a photopolymerization initiator; a radical crosslinking agent; The resin has a radical polymerizable group and a photodimerization reactive group. Photosensitive resin composition.

2. The photosensitive resin composition according to claim 1 , wherein the photodimerization reactive group is a group having a cinnamoyl structure.

3. The photosensitive resin composition according to claim 1 or 2, further comprising a compound B having an alkoxysilyl group.

4. 4. The photosensitive resin composition according to claim 3, wherein the compound B having an alkoxysilyl group has at least one group selected from the group consisting of a photodimerizable group and a radically polymerizable group.

5. The photosensitive resin composition according to claim 3 or 4, wherein the compound B having an alkoxysilyl group has an azole group.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound C having an azole group and at least one group selected from the group consisting of a radically polymerizable group and a photodimerization reactive group.

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a compound D having an azole group and not having an alkoxysilyl group, a radically polymerizable group, or a photodimerization reactive group.

8. The photosensitive resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

10. A laminate comprising two or more layers each made of the cured product according to claim 9, and a metal layer between any two adjacent layers made of the cured product.

11. A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of claims 1 to 8 onto a substrate to form a film.

12. The method for producing a cured product according to claim 11, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.

13. The method for producing a cured product according to claim 12 , further comprising, after the developing step, a second exposure step of exposing the pattern obtained by the developing step.

14. The method for producing a cured product according to any one of claims 11 to 13, comprising a heating step of heating the film at 50 to 450°C.

15. A semiconductor device comprising the cured product according to claim 9 or the laminate according to claim 10.

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