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

Abstract

Provided are: a resin composition containing a resin having a repeating unit having a specific structure and an ethylenically unsaturated group, and a polymerization initiator; a cured product obtained by curing the resin composition; a method for producing the cured product; a method for producing a laminate including the method for producing a cured product; and a method for producing a semiconductor device.

Description

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

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

[0002] Polyimides are used in a variety of fields, including semiconductor devices and aerospace.

[0003] Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble polyimide having a specific structure.

[0004] International Publication No. 2022 / 070946

[0005] One example of the application of polyimides is films used in semiconductor devices (e.g., insulating films such as interlayer insulating films for redistribution layers). Recently, with the increasing miniaturization and high integration of semiconductor devices, high resolution is required for resin compositions used to form these films.

[0006] An object of the present invention is to provide a resin composition having excellent resolution, a cured product obtained by curing the resin composition, a method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing a semiconductor device.

[0007] Examples of typical embodiments of the present invention are given below.

[0008] [1] A resin composition containing a resin having a repeating unit represented by the following formula (1-1) and having an ethylenically unsaturated group, and a polymerization initiator:

[0009]

[0010] In formula (1-1), X １ represents a tetravalent organic group, Y １ represents a divalent organic group. １ and Y １ At least one of the above includes at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4).

[0011]

[0012] The symbol * in formulas (2-1) to (2-4) indicates the bonding position to other atoms. [2] The resin composition according to [1], wherein the resin has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-2), a repeating unit represented by the following formula (1-3), and a repeating unit represented by the following formula (1-4):

[0013]

[0014] In formula (1-2), A ２ is -O- or -NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ２ represents a hydrogen atom or a monovalent organic group; X ２ represents a tetravalent organic group, Y ２ represents a divalent organic group. ３ is -O- or -NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ３ represents a hydrogen atom or a monovalent organic group; X ３ represents a tetravalent organic group, Y ３ represents a divalent organic group. ４１ and A ４２ are each independently —O— or —NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ４１ and R ４２ each independently represents a hydrogen atom or a monovalent organic group; X ４ represents a tetravalent organic group, Y ４ represents a divalent organic group. [3] The resin composition according to [1] or [2], wherein the resin has an imidization rate of 40% or more. [4] Y in the formula (1-1) １The resin composition according to any one of [1] to [3], wherein the value of Qa defined by the following formula (a) is 0.1 or more and 2.0 or less. Formula (a) Qa=Q １ / Q ２ Q １ Q is the number of groups selected from the group consisting of the group represented by the formula (2-1), the group represented by the formula (2-2), the group represented by the formula (2-3), and the group represented by the formula (2-4) in one molecule of the resin. ２ is the number of ethylenically unsaturated bonds in one molecule of the resin. [6] Y in the above formula (1-1) １The resin composition according to any one of [1] to [5], wherein the resin composition further contains an ethylenically unsaturated group. [7] The resin composition according to any one of [1] to [6], further containing a polymerizable compound. [8] The resin composition according to any one of [1] to [7], further containing a light absorber. [9] The resin composition according to [8], wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[10] The resin composition according to any one of [1] to [9], further containing an organic solvent.

[11] The resin composition according to any one of [1] to

[10] , wherein the resin composition is a negative-type photosensitive resin composition.

[12] The resin composition according to any one of [1] to

[11] , wherein the resin composition is used for forming an interlayer insulating film for a redistribution layer.

[13] A cured product obtained by curing the resin composition according to any one of [1] to

[12] .

[14] A method for producing a cured product, comprising: a film-forming step of applying the resin composition according to any one of [1] to

[12] onto a substrate to form a film; an exposure step of selectively exposing the film to light; and a development step of developing the film using a developer to form a pattern.

[15] A method for producing the cured product according to

[14] , comprising a heating step of heating the film at 50 to 450°C.

[16] A method for producing a laminate, comprising the method for producing the cured product according to

[14] .

[17] A method for producing a semiconductor device, comprising the method for producing the cured product according to

[14] .

[0015] According to the present invention, it is possible to provide a resin composition having excellent resolution, a cured product obtained by curing the resin composition, a method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing a semiconductor device.

[0016] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. 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 and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, 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, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and 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, for example, due to low solubility, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (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 another layer is 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 with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, 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, the composition may contain two or more compounds corresponding to each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. Unless otherwise specified herein, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment. In this specification, the term "organic group" refers to a group containing at least one carbon atom.

[0017] [Resin Composition] The resin composition of the present invention is a resin composition containing a resin having a repeating unit represented by the following formula (1-1) and having an ethylenically unsaturated group, and a polymerization initiator.

[0018]

[0019] In formula (1-1), X １ represents a tetravalent organic group, Y １ represents a divalent organic group. １ and Y １ At least one of the above includes at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4).

[0020]

[0021] In formulas (2-1) to (2-4), * indicates the bonding position to other atoms.

[0022] The resin composition of the present invention has excellent resolution. That is, the resin composition of the present invention can form a film with excellent resolution. While the mechanism by which the above-mentioned effects are achieved by the present invention is not fully understood, the inventors have hypothesized the following. However, the present invention is not limited in any way by the hypothesized mechanism below. Consider the case where a pattern is formed by selectively exposing a film formed from a photosensitive resin composition, curing the exposed areas to form image areas, and converting the unexposed areas to non-image areas. In this case, ideally, it is desirable that no light is irradiated onto the unexposed areas, but in reality, weak light hits the unexposed areas near the exposed areas (such areas are also referred to as "weakly exposed areas"). In the weakly exposed areas, a portion of the resin composition hardens, causing areas that should become non-image areas to become image areas, which is thought to result in reduced resolution. In the present invention, by using a resin having a specific structure, the reaction of radicals generated in the weakly exposed areas can be stopped, and high resolution can be achieved by suppressing the curing of the resin composition in the weakly exposed areas.

[0023] <Resin (A)> The resin composition of the present invention contains a resin (also referred to as "resin (A)") having a repeating unit represented by the following formula (1-1) and having an ethylenically unsaturated group.

[0024]

[0025] In formula (1-1), X １ represents a tetravalent organic group, Y １ represents a divalent organic group. １ and Y １ At least one of the above includes at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4).

[0026]

[0027] In formulas (2-1) to (2-4), * indicates the bonding position to other atoms.

[0028] Since the resin (A) has a repeating unit represented by the above formula (1-1), the resin (A) is a polyimide. The resin (A) may also be a precursor of a cyclized resin. The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure due to heat to become a cyclized resin, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors, with polyimide precursors being preferred.

[0029] X in formula (1-1) １ represents a tetravalent organic group. １ The tetravalent organic group represented by is preferably a tetravalent organic group containing an aromatic ring, more preferably a group represented by the following formula (5) or (6), and even more preferably a group represented by the following formula (5): In formulas (5) and (6), * represents the bonding position with -C(=O)- in formula (1-1).

[0030]

[0031] In formula (5), R １１２ is a single bond or a divalent linking group, and is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO ２ -, -NHCO-, and combinations thereof are preferred, and examples thereof include a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO ２ - is more preferably a group selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, a phenylene group, -O-, -CO-, -S- and -SO ２ It is more preferably a divalent group selected from the group consisting of -.

[0032] X １ Examples of X include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydrides. １ The tetracarboxylic acid dianhydride may contain only one kind of tetracarboxylic acid residue or two or more kinds of tetracarboxylic acid residues. The tetracarboxylic acid dianhydride is preferably represented by the following formula (O).

[0033]

[0034] In formula (O), R １１５ represents a tetravalent organic group. １１５ The preferred range of X １ The preferred range is the same as that of the above.

[0035] 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 2,3,3',4'-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 alkyl and alkoxy derivatives having 1 to 6 carbon atoms thereof.

[0036] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0037] From the viewpoint of film strength, X １ is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.

[0038] Y in formula (1-1) １ represents a divalent organic group. １ Examples of the divalent organic group represented by are 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 aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic heterocyclic group preferably contains one or more heteroatoms selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms as ring members. The number of ring members in the aromatic group is preferably 5 to 20, and more preferably 6 to 15. 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.

[0039] Y １ Examples of the group include a group represented by -Ar- or -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred. 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-, or -SO ２ - 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.

[0040] Y １ is preferably derived from a diamine. Examples of the diamine 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. １is preferably a diamine containing 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.

[0041]

[0042] In the formula, A represents a single bond or a divalent linking group, and is selected from the group consisting of 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—, and —SO ２ -, -NHCO-, or a group selected from a combination thereof, and 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 -SO ２ - is more preferably a group selected from -CH ２ -, -O-, -S-, -SO ２ -, -C(CF ３ ) ２ - or -C(CH ３ ) ２ In the formula, * represents the bonding position to other atoms.

[0043] 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'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 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 parafluoropropane, 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 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 can be mentioned.

[0044] Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017 / 038598.

[0045] 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.

[0046] Y １ is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of a film obtained using the resin composition of the present invention, wherein 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-, or -SO ２ 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 -SO ２ The aliphatic hydrocarbon group here is preferably an alkylene group.

[0047] Also, Y １From the viewpoint of i-line transmittance, it is also preferable that is a divalent organic group represented by the following formula (51) or the following formula (61). In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that is a divalent organic group represented by the following formula (61).

[0048]

[0049] 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 R is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents the bonding position to the nitrogen atom. 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).

[0050]

[0051] 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 position to a nitrogen atom. Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

[0052] Y １is preferably a diamine residue having at least two alkylene glycol units in the main chain (a group remaining after removal of the amino groups of the diamine) in order to more effectively suppress the occurrence of warping during firing. It is also preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

[0053] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both 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 Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0054] X １ and Y １ It is also preferable that at least one of Y １ Preferred examples of X 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). １ As the above, (DAA-1) to (DAA-5) are more preferred examples.

[0055] Resin (A) may be an alkali-soluble polyimide or a polyimide soluble in a developer primarily composed of an organic solvent, but is preferably a polyimide soluble in a developer primarily composed of an organic solvent. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38% by mass aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. In this specification, polyimide soluble in a developer primarily composed of an organic solvent refers to a polyimide that dissolves at 0.1 g or more in 100 g of cyclopentanone at 23° C. From the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferred, and a polyimide that dissolves at 1.0 g or more is even more preferred. The upper limit of the solubility is not particularly limited, but is preferably 100 g or less. From the viewpoint of the film strength and insulating properties of the resulting film, the resin (A) is preferably a polyimide having a plurality of imide structures in the main chain. In the present invention, the "main chain" refers to the relatively longest bonding chain in the resin molecule, and the "side chain" refers to the other bonding chains.

[0056] - Ethylenically unsaturated group - Resin (A) has an ethylenically unsaturated group. The ethylenically unsaturated group is a group having an ethylenically unsaturated bond. The ethylenically unsaturated bond means a polymerizable carbon-carbon double bond (C=C). When resin (A) has an ethylenically unsaturated group, the film obtained has excellent film strength. Resin (A) may have an ethylenically unsaturated group at the end of the main chain or on a side chain. The ethylenically unsaturated group is preferably radically polymerizable. The ethylenically unsaturated group may be contained in any part of resin (A), but is preferably present in X in formula (1-1). １ and Y １ The resin (A) is preferably contained in at least one of the following: １Examples of the ethylenically unsaturated group 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):

[0057]

[0058] 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.

[0059] In formula (IV), R ２１ represents an alkylene group having 2 to 12 carbon atoms, —O—CH ２ CH(OH)CH ２ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of repeating alkyleneoxy groups is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms), or a group 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, or 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.

[0060] 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).

[0061]

[0062] 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 the bonding position with other atoms; and ● represents the R ２１In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R in formula (IV). 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 formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 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 (e.g., 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 (e.g., glycidyl methacrylate).

[0063] In formula (IV), * represents the bonding position to another atom, and is preferably the bonding position to the main chain of resin (A).

[0064] The amount of ethylenically unsaturated bonds relative to the total mass of the resin (A) is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0065] -Fluorine Atom- From the viewpoint of the strength of the resulting film, it is also preferable that the resin (A) contains a fluorine atom. １ or Y １ and X １ or Y １The amount of fluorine atoms relative to the total mass of the resin (A) is preferably 5% by mass or more and 20% by mass or less. The amount of fluorine atoms relative to the total mass of the resin (A) may be 10% by mass or more.

[0066] -Silicon Atom- From the viewpoint of the strength of the resulting film, it is also preferable that the resin (A) contains a silicon atom. The silicon atom can be, for example, X １ or Y １ It is more preferable that the silicon atom or the organically modified (poly)siloxane structure is contained in the polyimide. 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 resin (A). The amount of silicon atoms relative to the total mass of the resin (A) is preferably 1 mass% or more, and more preferably 20 mass% or less.

[0067] -Polymerizable Group Other Than Ethylenically Unsaturated Group- The resin (A) may have a polymerizable group other than an ethylenically unsaturated group. Examples of the polymerizable group other than an ethylenically unsaturated group 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. Examples of the polymerizable group other than an ethylenically unsaturated group include, for example, Y １ The amount of polymerizable groups other than ethylenically unsaturated groups relative to the total mass of the resin (A) is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0068] - Polarity conversion group - The resin (A) may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the resin (A) 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. However, 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. The polarity conversion group is, for example, X １ , Y １ , or at the terminal of the resin (A). When the resin (A) has an acid-decomposable group, the resin composition may contain a photoacid generator. From such a resin composition, for example, a chemically amplified positive-working photosensitive film or negative-working photosensitive film is formed.

[0069] -Acid Value- When the resin (A) is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the resin (A) 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. When the resin (A) is subjected to development using a developer containing an organic solvent as a main component (e.g., "organic solvent development"), the acid value of the resin (A) is preferably 1 to 35 mgKOH / g, more preferably 2 to 30 mgKOH / g, and even more preferably 5 to 20 mgKOH / g. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. From the viewpoint of achieving both storage stability and developability, the acid group contained in resin (A) preferably has a pKa of 0 to 10, more preferably 3 to 8. pKa refers to 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 refers to a value calculated using ACD / ChemSketch (registered trademark) unless otherwise specified. For pKa, reference may be made to the value listed in the "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, resin (A) preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.

[0070] -Phenol Hydroxy Group- From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the resin (A) preferably has a phenolic hydroxy group. The resin (A) may have the phenolic hydroxy group at the end of the main chain or on a side chain. The phenolic hydroxy group can be, for example, X １ or Y １The amount of phenolic hydroxy groups relative to the total mass of the resin (A) is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0071] To improve adhesion to the substrate, the resin (A) 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.

[0072] In order to improve the storage stability of the resin composition, it is also preferable that the main chain terminals of the resin (A) 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 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.

[0073] Resin (A) is X in formula (1-1) １ and Y １ At least one of the above contains at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4): The group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4) are considered to have a polymerization inhibiting effect and to be able to stop the reaction between radicals generated in the weakly exposed area and ethylenically unsaturated groups in the resin (A).

[0074]

[0075] * in formulas (2-1) to (2-4) indicates the bonding position with other atoms. Here, "other atoms" refers to atoms other than the atoms included in formulas (2-1) to (2-4) marked with *, and may be hydrogen atoms, atoms included in other formulas (2-1) to (2-4), or atoms included in any substituent. For example, "other atoms" refers to X in formula (1-1). １ The carbon atom of the carbonyl group bonded to Y １ It may also be a nitrogen atom bonded to X. １ When X contains a group represented by any one of formulas (2-1) to (2-4), １ The atoms contained in the partial structure other than the group represented by any one of formulas (2-1) to (2-4) in X may be "other atoms." １ When Y contains two or more groups represented by any one of formulas (2-1) to (2-4), one group represented by any one of formulas (2-1) to (2-4) may be bonded to another group represented by any one of formulas (2-1) to (2-4). １ When Y contains a group represented by any one of formulas (2-1) to (2-4), １ The atoms contained in the partial structure other than the group represented by any one of formulas (2-1) to (2-4) in Y may be "other atoms." １contains two or more groups represented by any one of formulas (2-1) to (2-4), one group represented by any one of formulas (2-1) to (2-4) may be bonded to another group represented by any one of formulas (2-1) to (2-4).

[0076] Resin (A) is Y in formula (1-1) １ It is preferable that the compound represented by the formula (2-1) contains at least one selected from the group consisting of a group represented by the formula (2-2), a group represented by the formula (2-3), and a group represented by the formula (2-4).

[0077] For the resin (A), the value of Qa defined by the following formula (a) is preferably 0.1 or more and 2.0 or less, more preferably 0.3 or more and 1.5 or less, and even more preferably 0.5 or more and 1.0 or less. When the value of Qa is 2.0 or less, the film residual rate, which is the ratio of the film thickness after curing to the film thickness before curing of the film formed using the resin composition of the present invention, is increased, which is preferable. When the value of Qa is 0.1 or more, the resolution is improved, which is preferable. Formula (a) Qa = Q １ / Q ２ Q １ Q is the number of groups selected from the group consisting of groups represented by formula (2-1), groups represented by formula (2-2), groups represented by formula (2-3), and groups represented by formula (2-4) in one molecule of resin (A). ２ is the number of ethylenically unsaturated bonds in one molecule of resin (A).

[0078] Q １ and Q ２ The value of Q can be determined by dissolving the resin composition in a solvent for NMR (Nuclear Magnetic Resonance) such as deuterated dimethyl sulfoxide (DMSO) and measuring proton NMR. １ and Q ２ It can be calculated from the peak ratio for

[0079] The value of Qa can be adjusted, for example, by adjusting the amounts of a monomer having a group selected from the group consisting of a group represented by formula (2-1), a group represented by formula (2-2), a group represented by formula (2-3), and a group represented by formula (2-4) and a monomer having an ethylenically unsaturated group when synthesizing resin (A). Alternatively, the value of Qa can be adjusted after synthesizing the resin by a method of introducing at least one of a group selected from the group consisting of a group represented by formula (2-1), a group represented by formula (2-2), a group represented by formula (2-3), and a group represented by formula (2-4) and an ethylenically unsaturated group into the resin.

[0080] Resin (A) may contain only one type of repeating unit represented by formula (1-1), or may contain two or more types. The content of repeating units represented by formula (1-1) in resin (A) is preferably 50 mol % or more and 100 mol % or less, and more preferably 70 mol % or more and 100 mol % or less, based on the total repeating units in resin (A).

[0081] Resin (A) may further have other types of repeating units in addition to the repeating unit represented by formula (1-1). For example, resin (A) may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-2) below, repeating units represented by formula (1-3) below, and repeating units represented by formula (1-4) below. A repeating unit selected from the group consisting of repeating units represented by formula (1-2) below, repeating units represented by formula (1-3) below, and repeating units represented by formula (1-4) below is also referred to as a "repeating unit (PA)".

[0082]

[0083] In formula (1-2), A ２ is -O- or -NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ２ represents a hydrogen atom or a monovalent organic group; X ２ represents a tetravalent organic group, Y ２ represents a divalent organic group. ３ is -O- or -NR Ｚrepresents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ３ represents a hydrogen atom or a monovalent organic group; X ３ represents a tetravalent organic group, Y ３ represents a divalent organic group. ４１ and A ４２ are each independently —O— or —NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ４１ and R ４２ each independently represents a hydrogen atom or a monovalent organic group; X ４ represents a tetravalent organic group, Y ４ represents a divalent organic group.

[0084] A in formula (1-2) ２ is -O- or -NR Ｚ R represents -, and preferably represents -O-. Ｚ represents a hydrogen atom or a monovalent organic group, and preferably represents a hydrogen atom.

[0085] R in formula (1-2) ２ 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. ２ Preferably, R contains a polymerizable group. ２ It is also preferable that the copolymer contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include an ethylenically unsaturated group, 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, and an ethylenically unsaturated group is preferred. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and a group represented by the following formula (III) is preferred.

[0086]

[0087] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably represents a hydrogen atom or a methyl group. In formula (III), * represents the bonding position to other atoms. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a 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 a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0088] R in formula (1-2) ２represents a hydrogen atom, the resin (A) 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.

[0089] R in formula (1-2) ２ However, it may also 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. However, 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.

[0090] X in formula (1-2) ２ represents a tetravalent organic group. ２ The explanation, specific examples and preferred ranges of X in the above formula (1-1) １ It is the same as in

[0091] Y in formula (1-2) ２ represents a divalent organic group. ２ The description, specific examples and preferred ranges of Y in the above formula (1-1) are １ It is the same as in

[0092] However, the repeating unit represented by formula (1-2) is X ２ and Y ２ At least one of the above may or may not contain at least one selected from the group consisting of a group represented by formula (2-1), a group represented by formula (2-2), a group represented by formula (2-3), and a group represented by formula (2-4).

[0093] A in formula (1-3)３ is -O- or -NR Ｚ R represents -, and preferably represents -O-. Ｚ represents a hydrogen atom or a monovalent organic group, and preferably represents a hydrogen atom.

[0094] R in formula (1-3) ３ represents a hydrogen atom or a monovalent organic group. ３ The explanation, specific examples and preferred ranges of R in the above formula (1-2) are as follows: ２ It is the same as in

[0095] X in formula (1-3) ３ represents a tetravalent organic group. ３ The explanation, specific examples and preferred ranges of X in the above formula (1-1) １ It is the same as in

[0096] Y in formula (1-3) ３ represents a divalent organic group. ３ The description, specific examples and preferred ranges of Y in the above formula (1-1) are １ It is the same as in

[0097] However, the repeating unit represented by formula (1-3) is X ３ and Y ３ At least one of the above may or may not contain at least one selected from the group consisting of a group represented by formula (2-1), a group represented by formula (2-2), a group represented by formula (2-3), and a group represented by formula (2-4).

[0098] A in formula (1-4) ４１ and A ４２ are each independently —O— or —NR Ｚ R represents -, and preferably represents -O-. Ｚ represents a hydrogen atom or a monovalent organic group, and preferably represents a hydrogen atom.

[0099] R in formula (1-4) ４１ and R ４２ R each independently represents a hydrogen atom or a monovalent organic group. ４１ and R ４２ The explanation, specific examples and preferred ranges of R in the above formula (1-2) are as follows: ２It is the same as in

[0100] X in formula (1-4) ４ represents a tetravalent organic group. ４ The explanation, specific examples and preferred ranges of X in the above formula (1-1) １ It is the same as in

[0101] Y in formula (1-4) ４ represents a divalent organic group. ４ The description, specific examples and preferred ranges of Y in the above formula (1-1) are １ It is the same as in

[0102] However, the repeating unit represented by formula (1-4) is X ４ and Y ４ At least one of the above may or may not contain at least one selected from the group consisting of a group represented by formula (2-1), a group represented by formula (2-2), a group represented by formula (2-3), and a group represented by formula (2-4).

[0103] When the resin (A) has the repeating unit (PA), it may contain only one type of repeating unit (PA), or may contain two or more types of repeating units (PA). When the resin (A) has the repeating unit (PA), the content of the repeating unit (PA) in the resin (A) is preferably 50 mol % or less, and more preferably 30 mol % or less, based on the total repeating units in the resin (A).

[0104] -Imidization rate (ring closure rate)- The imidization rate (also referred to as "ring closure rate") of the resin (A), which is the ratio of the film thickness after curing to the film thickness before curing of a film formed using the resin composition of the present invention, is preferably 40% or more, more preferably 70% or more, and even more preferably 90% or more, because this increases the residual rate of the film. The upper limit of the imidization rate of the resin (A) is not particularly limited, and may be 100% or less.

[0105] In the present invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Examples of such solvents include solvents contained in the resin composition, such as NMP (N-methyl-2-pyrrolidone). The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of 15 μm after film formation on the silicon wafer. Here, if only a resin solution with a low viscosity is obtained and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be adjusted as appropriate. For example, if the film thickness is 5 μm or greater, a similar imidization rate value can be obtained. The resin layer was measured by an ATR (Attenuated Total Reflection) method using a Nicoleti S20 (manufactured by Thermo Fisher) in the measurement range of 4000 to 700 cm －１ , the measurement is performed 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１The imidization index A of the resin is calculated by dividing the imidization index B by the peak height of the peak (the peak with the greatest intensity in the case of multiple peaks) in a nitrogen atmosphere at a heating rate of 10°C / min and heated at 350°C for 1 hour. The imidization index B is calculated in the same manner for a film obtained by heating at 350°C for 1 hour. The imidization index A is then divided by the imidization index B to calculate the imidization rate of the resin. In measuring the imidization rate, the resin whose imidization rate is to be measured can be obtained from the resin composition by, for example, the following method. A solution of 1 g of the resin composition and 2 g of THF (tetrahydrofuran) is added to 50 g of methanol or water to cause crystallization, and the resin is precipitated and filtered. The residue is recovered, dissolved in 3.0 g of THF, and added to 50 g of methanol or water to cause crystallization. The crystallization is then filtered and dried at 40°C for 20 hours to obtain the resin. When measuring the physical properties of the resin, such as absorbance, acid value, and amine value, the resin can be obtained and measured by the same method.

[0106] Resin (A) (polyimide) 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, preparing 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, preparing a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid to 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.

[0107] The weight average molecular weight (Mw) of the resin (A) is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain a film with excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more. The number average molecular weight (Mn) of the resin (A) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the resin (A) 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 resin (A) is not particularly specified, but is 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 of the present invention contains multiple types of resins (A), it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of resin (A) are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating multiple types of resins (A) as one resin are each within the above ranges.

[0108] [Content] The content of resin (A) 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. Furthermore, the content of resin (A) 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 type of resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0109] <Other Resins> The resin composition of the present invention may contain, in addition to the resin (A), another resin different from the resin (A) (hereinafter, simply referred to as "other resin"). Examples of the other resin include phenolic resins, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, polybenzoxazole, polyimides, polyamides, and polyimideamides. 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 below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can 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).

[0110] When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. The content of the other resin 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. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above 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, even 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, as long as it is 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.

[0111] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound (crosslinking agent). Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0112] [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 containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0113] 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. The radical crosslinking agent may 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. From the viewpoint of the film strength of the obtained 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.

[0114] 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.

[0115] 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 group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0116] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0117] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0118] 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.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0119] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an ester include 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).

[0120] 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. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0121] 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 obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0122] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more 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. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0123] As the radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferred. When the resin composition contains crosslinking agent U, chemical resistance, resolution, etc. may be improved. Examples of crosslinking agent U include the compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064, the contents of which are incorporated herein by reference.

[0124] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. 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, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 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, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates 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 approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents 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. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0125] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, more preferably 5% by mass or more, and more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total solid content of the resin composition.

[0126] 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.

[0127] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. The other crosslinking agent is preferably a compound having, in its molecule, a plurality of groups that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or a base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. The other crosslinking agent is preferably a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group, and more preferably a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom. Furthermore, the other crosslinking agent preferably has a total of two or more acyloxymethyl groups, methylol groups, ethylol groups, and alkoxymethyl groups. Among these, compounds having two or more acyloxymethyl groups, compounds having two or more methylol groups, compounds having two or more ethylol groups, or compounds having two or more alkoxymethyl groups are more preferred. Examples of other crosslinking agents include 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, methylol group, ethylol group, or 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. Oligomers formed by self-condensation of 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.

[0128] 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.

[0129] -Epoxy Compound (Compound Having Epoxy Group)- 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 and suppressing warpage.

[0130] The epoxy compound preferably contains a polyethylene oxide group, which further reduces the modulus of elasticity and suppresses warpage. The polyethylene oxide group refers to a group having two or more repeating ethylene oxide units, and preferably has 2 to 15 repeating units.

[0131] 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, the same applies hereinafter) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark, the same applies below) BEO-20E, Rikaresin BEO-60E, Rikaresin HBE-100, Rikaresin DME-100, Rikaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Epolead (registered trademark, the same applies hereinafter) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead (registered trademark, the same applies hereinafter) GT401, Epolead PB4700, Epolead PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-30 00-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like.The following compounds are also preferably used:

[0132]

[0133] In the formula, n is an integer of 1 to 5, and m is an integer of 1 to 20.

[0134] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in order to achieve both improved heat resistance and improved elongation.

[0135] -Oxetane Compound (Compound Having an Oxetanyl Group)- Examples of the oxetane compound 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 include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more.

[0136] - Benzoxazine Compound (Compound Having a Benzoxazolyl Group) - Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, thermal shrinkage is reduced, thereby suppressing the occurrence of warping.

[0137] Preferred examples of the benzoxazine compound 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. These may be used alone or in combination of two or more.

[0138] The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. 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 amount thereof is preferably within the above range.

[0139] [Polymerization initiator] The resin composition of the present invention contains a polymerization initiator (also referred to as "initiator"). The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator. The photopolymerization initiator may be a photoradical polymerization initiator or a photoacid generator.

[0140] (Photoradical polymerization initiator) The photoradical polymerization initiator is not particularly limited and 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 with a photoexcited sensitizer to generate active radicals.

[0141] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0142] Any known compound can be used as the photoradical polymerization initiator. 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 oxide, hexaarylbiimidazole, 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 of these compounds, please refer to 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 can be mentioned, the contents of which are incorporated herein by reference.

[0143] 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. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0144] 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.

[0145] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0146] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0147] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0148] 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.

[0149] 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) described compounds, 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.

[0150] Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0151]

[0152] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), 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), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0153]

[0154] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, as described in paragraphs 0169 to 0171 of WO 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom. Also, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a carbazole skeleton to which a substituent having a hydroxy group is bonded, as described in paragraphs 0208 to 0210 of WO 2021 / 020359, can also be used. The contents of these compounds are incorporated herein by reference. Additionally, compounds described in paragraphs 0113 to 0117 of JP 2023-058585 A can also be used as photopolymerization initiators. This description is incorporated herein by reference.

[0155] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. 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. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0156] [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 undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or 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, p-dimethylaminobenzylideneindanone, and 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, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 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, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0157] 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 still 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.

[0158] [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 those having -S-S-, -SO ２ Compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthate compounds, and the like having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization can be used. These compounds can donate hydrogen to a low-activity radical to generate a radical, or can be oxidized and then deprotonated to generate a radical. In particular, thiol compounds can be preferably used.

[0159] 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.

[0160] When the resin composition 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. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0161] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators 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 a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in 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 is not particularly limited, and known base generators can be used. Examples of known base generators 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, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Examples of base generators include the compounds described in paragraphs 0249 to 0275 of Publication No. 2022 / 145355. The above descriptions are incorporated herein by reference.

[0162] Examples of the base generator include, but are not limited to, the following compounds:

[0163]

[0164] 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.

[0165] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0166] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0167]

[0168] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0169]

[0170] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. 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, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0171] <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.

[0172] 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 (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, 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.

[0173] 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.

[0174] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0175] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0176] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0177] 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.

[0178] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0179] 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.

[0180] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0181] In the present invention, one solvent selected from 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, 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 a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as resin (A) contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0182] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount of the solvents is preferably within the above range.

[0183] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0184] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the 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.

[0185]

[0186] 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- (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-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0187] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0188] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0189] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of resin (A). By ensuring that the content is equal to or greater than the above 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 above upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, 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.

[0190] <Polymerization Inhibitor> The resin composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0191] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine, the contents of which are incorporated herein by reference.

[0192] 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%, based on the total solid content of the resin composition.

[0193] 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.

[0194] <Other Additives> The resin composition of the present invention may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, light absorbers, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.). By appropriately incorporating these components, properties such as film physical properties can be adjusted. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are blended, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0195] [Surfactant] Various surfactants can be used as the surfactant, 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.

[0196] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be 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 containing a surfactant, 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 uniform film with little thickness unevenness.

[0197] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds 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 examples thereof include the following compounds.

[0198]

[0199] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 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.

[0200] 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.

[0201] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0202] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0203] [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 drying after application.

[0204] In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0205] When the resin composition 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. 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.

[0206] [Thermal Polymerization Initiator] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals by thermal energy and initiate or promote the polymerization reaction of a polymerizable compound. Addition of 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, photopolymerization initiators may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

[0207] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0208] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, 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, it is preferable that the total amount is in the above range.

[0209] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0210] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 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. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0211] [Ultraviolet absorber] Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. Specific examples of the ultraviolet absorber include the compounds described in paragraphs 0341 to 0342 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0212] The ultraviolet absorbers may be used singly or in combination of two or more. When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid mass of the resin composition.

[0213] [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.

[0214] 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 organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0215] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0216] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of resin (A). When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is improved.

[0217] [Antioxidant] By including an antioxidant as an additive, the elongation properties of the cured film and adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348 to 0357 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0218] The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of resin (A). By adding an amount of 0.1 part by mass or more, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials even in high-temperature, high-humidity environments, and by adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, by interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.

[0219] [Anti-aggregating Agent] Examples of the anti-aggregating agent include sodium polyacrylate.

[0220] The anti-aggregating agent may be used singly or in combination of two or more. When the resin composition contains an anti-aggregating agent, the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total mass of the solid content of the resin composition.

[0221] [Phenol-based compounds] Examples of phenol-based compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0222] The phenolic compound may be used alone or in combination of two or more. When the resin composition contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0223] [Other Polymer Compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified compounds into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0224] The other polymer compounds may be used singly or in combination of two or more. When the resin composition contains the other polymer compounds, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid mass of the resin composition.

[0225] [Light absorber] The resin composition of the present invention may further contain a light absorber (a compound whose absorbance at the exposure wavelength is reduced by exposure). Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.

[0226] In addition, a preferred embodiment of the present invention is to include a photochromic compound as a light absorber. A photochromic compound is a compound whose absorption spectrum changes as a result of a change in the molecular geometric structure upon absorption of light. Specific examples of photochromic compounds are shown below, but the present invention is not limited to these.

[0227]

[0228] The light absorber is preferably at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.

[0229] When the resin composition of the present invention contains a light absorber, the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0230] The resin composition of the present invention is preferably a negative photosensitive resin composition, and is preferably used to form an interlayer insulating film for a rewiring layer.

[0231] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is 1 / s or less, a coating film having excellent coating surface condition can be obtained.

[0232] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0233] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0234] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0235] Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0236] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0237] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited, and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0238] <Characteristics of cured product of resin composition> The imidization rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0239] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0240] For the purpose of removing foreign matter such as dust and fine particles from the resin composition of the present invention, filtration using a filter is preferably performed. Regarding filtration using a filter, the contents described in paragraph

[0287] of WO 2023 / 190064 are incorporated herein by reference.

[0241] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0242] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition to a substrate to form a film.

[0243] [Substrate] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0244] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0245] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0246] <Drying Step> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film-forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be carried out under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0247] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0248] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0249] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line); (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0250] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0251] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0252] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0253] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0254] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph

[0387] of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0255] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0256] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0257] When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates into the pattern, the performance of the pattern, such as breaking elongation, may be improved.

[0258] As the basic compound, from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated), an organic base is preferred. As the basic compound, a basic compound having an amino group is preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. However, to promote the imidization reaction, primary amines, secondary amines, tertiary amines, or ammonium salts are preferred, secondary amines, tertiary amines, or ammonium salts are more preferred, secondary amines or tertiary amines are even more preferred, and tertiary amines are particularly preferred. As the basic compound, from the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferred that it is difficult for the amount remaining to decrease before heating due to vaporization, etc., is preferred. Therefore, the boiling point of the basic compound is preferably 30°C to 350°C at normal pressure (101,325 Pa), more preferably 80°C to 270°C, and even more preferably 100°C to 230°C. The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer. For example, when the boiling point of the organic solvent is 100° C., the boiling point of the basic compound used is preferably 80° C. or higher, and more preferably 100° C. or higher. The developer may contain only one type of basic compound, or may contain two or more types.

[0259] Specific examples of the basic compound 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, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples of the alkyl ester include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

[0260] The preferred embodiments of the base generator are the same as those of the base generator contained in the composition described above. In particular, the base generator is preferably a thermal base generator.

[0261] When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the developer. The developer may contain only one type of basic compound or base generator, or two or more types. When two or more types of at least one of the basic compound and base generator are used, the total content thereof is preferably within the above-mentioned range.

[0262] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0263] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0264] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0265] [Rinse Liquid] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0266] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse solution is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0267] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), or propylene glycol monomethyl ether (PGME), more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0268] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, and may also account for 100% by mass of the total mass of the rinse solution.

[0269] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0270] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0271] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0272] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0273] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0274] The treatment liquid may include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator. Preferred aspects of the organic solvent, the basic compound, and the base generator are the same as the preferred aspects of the organic solvent, the basic compound, and the base generator used in the rinse liquid described above. The treatment liquid can be supplied to the pattern using the same method as the rinse liquid described above, and preferred aspects are also the same.

[0275] The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the treatment liquid. There is no particular limitation on the lower limit of the content, but it is preferably, for example, 0.1% by mass or more. Furthermore, when the basic compound or base generator is solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is also preferably 70 to 100% by mass, relative to the total solid content of the treatment liquid. When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types. When there are two or more types of at least one of the basic compound and the base generator, it is preferable that the total amount thereof is within the above-mentioned range.

[0276] <Heating Step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) is preferably subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention preferably includes a heating step in which the pattern obtained in the development step is heated. The method for producing a cured product of the present invention may also include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained in the film formation step is heated. In the heating step, a resin such as a polyimide precursor is cyclized to form a resin such as a polyimide. Crosslinking of unreacted crosslinkable groups in the resin (A) or a crosslinking agent other than the resin (A) also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0277] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0278] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0279] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0280] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0281] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0282] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0283] The heating step is preferably carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, from the viewpoint of preventing decomposition of the resin (A). The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0284] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0285] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0286] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0287] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0288] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0289] <Applications> Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0290] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0291] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0292] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0293] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring, such as a rewiring layer.

[0294] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0295] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0296] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0297] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0298] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. The contents of this specification are incorporated herein by reference.

[0299] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0300] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0301] <Resin Synthesis Example> (Synthesis of A-1) 20.0 g (38.4 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 7.23 g (33.4 mmol) of 4,4'-diamino-3,3'-dihydroxybiphenyl were dissolved in 125 ml of NMP and stirred at 200°C for 4 hours under a nitrogen atmosphere to obtain a polyimide solution. Next, 0.1 g of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 2.59 g (16.7 mmol) of MOI (2-isocyanatoethyl methacrylate) were added to the polyimide solution at room temperature (23°C), and the temperature was raised to 60°C. After that, 0.1 g of Neostan U-600 (Nitto Kasei Co., Ltd., inorganic bismuth) was added and the mixture was stirred for 3 hours. Next, 375 ml of THF was added to the polyimide solution, and the mixture was added dropwise to 1500 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain polyimide (A-1) as a powder.

[0302] (Synthesis of A-3, A-4, A-5, A-9, A-10, and B-1) A-3, A-4, A-5, A-9, A-10, and B-1 were synthesized in the same manner as A-1.

[0303] (Synthesis of A-2) 10.6 g (34.0 mmol) of 4,4'-oxydiphthalic dianhydride and 8.84 g (68.0 mmol) of 2-hydroxyethyl methacrylate were dissolved in 50 ml of diglyme, and 18.7 g (135 mmol) of pyridine was added and stirred at 60°C for 4 hours to obtain a mixture. The resulting mixture was then cooled to 0°C, and 8.09 g (68.0 mmol) of thionyl chloride was added dropwise over 15 minutes. The mixture was stirred for 1 hour to obtain a white precipitate of pyridinium hydrochloride. A solution of 7.90 g (30.6 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane in 50 ml of NMP was then added dropwise over 30 minutes to obtain a mixture. The resulting mixture was stirred at room temperature for 1 hour, and 8 ml of ethanol was added. The mixture was further stirred for another 1 hour to obtain a solution. The resulting solution was added dropwise to 1,000 ml of water to precipitate a polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain powder A-2'. Next, the obtained A-2' was dissolved in 100 ml of NMP, and 13.6 g (71.0 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDCI) hydrochloride, 2.63 g (30.6 mmol) of methacrylic acid, and 6.13 g (30.6 mmol) of 4-carboxy-TEMPO were added sequentially, and the mixture was stirred for 24 hours. 375 ml of THF was added to the obtained polyimide solution, and the mixture was added dropwise to 1500 ml of water to precipitate the polymer. The polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain powder A-2. 30 g of A-2'' was dispersed in 1000 ml of water, stirred at 70°C for a predetermined time, and the polymer collected by filtration was dried under reduced pressure at 40°C for 1 day to obtain powder A-2. The predetermined time is the time at which the imidization rate of the polymer sampled by filtration reaches 50% as calculated by the method described above.

[0304] (Synthesis of A-6, A-7, and A-11) A-6, A-7, and A-11 were synthesized in the same manner as A-2.

[0305] (Synthesis of A-8) 48.7 g (225 mmol) of 3,3'-dihydroxybenzidine and 375 mL of dimethylformamide were mixed in a 1 L flask. Under ice cooling, 98.2 g (450 mmol) of di-t-butyl dicarbonate was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 60°C for 5 hours. After the reaction was completed and the mixture was cooled to room temperature, 35 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 68.7 g (450 mmol) of p-chloromethylstyrene, 74.6 g (540 mmol) of potassium carbonate, and 8.96 g (54.0 mmol) of potassium iodide were added, and the mixture was stirred at 60°C for 3 hours. After the reaction was completed, filtration was performed by suction filtration, and the filtrate was added dropwise to 500 mL of water. White crystals precipitated, and the precipitated solid was collected by suction filtration. The resulting white solid was purified by recrystallization using 1000 mL of acetone at 60°C to obtain intermediate A-8a. Next, 75.0 g (116 mmol) of A-8a and 500 mL of methylene chloride were mixed in a 1 L flask. 132 g (1156 mmol) of trifluoroacetic acid was added at room temperature, and then the mixture was stirred at 40°C for 5 hours. After completion of the reaction, 250 mL of methanol and then 117 g (1156 mmol) of triethylamine were added dropwise under ice cooling. Pale yellow crystals were precipitated, and the precipitated solid was recovered by suction filtration. The mixture was suspended and washed in 750 mL of methanol to obtain diamine A-8b. 30.0 g (57.6 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 2.19 g (10.1 mmol) of 3,3'-dihydroxybenzidine and 18.2 g (40.6 mmol) of A-8b were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at a temperature of 0 to 10°C. After stirring at 25°C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added and the mixture was allowed to react at 80°C for 4 hours. 500 ml of THF was added to the obtained polyimide solution, and the mixture was added dropwise to 2000 ml of methanol to precipitate the polymer. The polymer collected by filtration was dried at 40° C. under reduced pressure for 1 day to obtain polyimide (A-8) as a powder.

[0306] Examples and Comparative Examples In each example and comparative example, the components listed in Tables 1 and 2 below were mixed to obtain a resin composition. The content of each component other than the solvent listed in Tables 1 and 2 was the amount (parts by mass) listed in the "Parts by Mass" column. When two or more compounds were used as each component, the "type" and "parts by mass" were listed, separated by a " / ". In these columns, the order of the entries separated by a " / " corresponds to each other. The amount of solvent used was adjusted to achieve the solid content concentration listed in the "Solid Content Concentration (% by Mass)" column in Tables 1 and 2. Tables 1 and 2 list the "type" and "mass ratio" of the solvent used. The "mass ratio" of the solvent is the content (% by mass) of each type of solvent relative to the total solvent. In Tables 1 and 2, a "-" indicates that the resin composition did not contain the corresponding component. The resulting resin composition was pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. The resulting resin composition was used as a negative-tone photosensitive resin composition.

[0307] Tables 1 and 2 show the imidization rates of the resins. When two or more types of compounds were used as the resin, the imidization rates were listed separated by " / ". The order in which the "type" and "imidization rate" separated by " / " were listed corresponds to each other. The imidization rate was determined by the method described above. Tables 1 and 2 also show the value of Qa, defined by the following formula (a), for the resin. When two or more types of compounds were used as the resin, the value of Qa was listed separated by " / ". The order in which the "type" and "Qa value" separated by " / " were listed corresponds to each other. Formula (a) Qa=Q １ / Q ２ Q １ Q is the number of groups selected from the group consisting of groups represented by formula (2-1), groups represented by formula (2-2), groups represented by formula (2-3), and groups represented by formula (2-4) in one molecule of the resin. ２ is the number of ethylenically unsaturated bonds in one resin molecule.

[0308]

[0309]

[0310] Details of each component listed in the above table are as follows:

[0311] <Resin> The structural formulas of the compounds used as resins are shown below. For resins having two or more types of repeating units enclosed in [ ], the molar ratio (mol %) of each repeating unit relative to all repeating units is written as a subscript to the right of [ ].

[0312]

[0313] A-1 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a hydrogen atom. With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the hydrogen atoms bonded to *1, the proportion of the ethylenically unsaturated group represented by formula (EC1) is 50 mol %, and the proportion of the hydrogen atoms bonded to *1 is 50 mol %.

[0314]

[0315] A-2 is a resin having a main chain formed by randomly bonding repeating units bracketed in [ ]. The molar ratios (mol %) of each repeating unit, a, b, c, and d, are a+b+c+d=100, and (2a+b+c):(2d+b+c)=50:50. *1 and *2 in the above formula indicate bonding positions, and *1 and *2 are bonded. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC2) or a group represented by formula (EC3). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC2) and the group represented by formula (EC3), the proportion of the ethylenically unsaturated group represented by formula (EC2) is 50 mol %, and the proportion of the group represented by formula (EC3) is 50 mol %.

[0316]

[0317] A-3 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a group represented by formula (EC4). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the group represented by formula (EC4), the proportion of the ethylenically unsaturated group represented by formula (EC1) is 50 mol %, and the proportion of the group represented by formula (EC4) is 50 mol %.

[0318]

[0319] A-4 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a group represented by formula (EC5). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the group represented by formula (EC5), the proportion of the ethylenically unsaturated group represented by formula (EC1) is 50 mol %, and the proportion of the group represented by formula (EC5) is 50 mol %.

[0320]

[0321] A-5 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a hydrogen atom. With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the hydrogen atoms bonded to *1, the proportion of the ethylenically unsaturated group represented by formula (EC1) is 20 mol %, and the proportion of the hydrogen atoms bonded to *1 is 80 mol %.

[0322]

[0323] A-6 is a resin having a main chain formed by randomly bonding repeating units bracketed in [ ]. The molar ratios (mol %) of each repeating unit, a, b, c, and d, are a+b+c+d=100, and (2a+b+c):(2d+b+c)=85:15. *1 and *2 in the above formula indicate bonding positions, and *1 and *2 are bonded. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC2) or a group represented by formula (EC3). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC2) and the group represented by formula (EC3), the proportion of the ethylenically unsaturated group represented by formula (EC2) is 50 mol %, and the proportion of the group represented by formula (EC3) is 50 mol %.

[0324]

[0325] A-7 is a resin having a main chain formed by randomly bonding repeating units bracketed in [ ]. The molar ratios (mol %) of a, b, c, and d of each repeating unit are a+b+c+d=100, and (2a+b+c):(2d+b+c)=30:70. *1 and *2 in the above formula indicate bonding positions, and *1 and *2 are bonded. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC2) or a group represented by formula (EC3). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC2) and the group represented by formula (EC3), the proportion of the ethylenically unsaturated group represented by formula (EC2) is 50 mol %, and the proportion of the group represented by formula (EC3) is 50 mol %.

[0326]

[0327] A-8 is a resin having a main chain in which repeating units enclosed in brackets [ ] are randomly bonded.

[0328]

[0329] A-9 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a hydrogen atom. With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the hydrogen atoms bonded to *1, the proportion of the ethylenically unsaturated group represented by formula (EC1) is 33 mol %, and the proportion of the hydrogen atoms bonded to *1 is 67 mol %.

[0330]

[0331] A-10 is a resin having a main chain made up of repeating units bracketed in [ ]. In the above formula, *1 and *2 indicate bonding positions, and *1 and *2 are bonded together. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC1) or a hydrogen atom. With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC1) and the hydrogen atoms bonded to *1, the proportion of the ethylenically unsaturated group represented by formula (EC1) is 91 mol %, and the proportion of the hydrogen atoms bonded to *1 is 9 mol %.

[0332]

[0333] A-11 is a resin having a main chain formed by randomly bonding repeating units bracketed in [ ]. The molar ratios (mol %) of a, b, c, and d of each repeating unit are a+b+c+d=100, and (2a+b+c):(2d+b+c)=40:60. *1 and *2 in the above formula indicate bonding positions, and *1 and *2 are bonded. That is, *1 in the repeating unit bracketed in [ ] is bonded to an ethylenically unsaturated group represented by formula (EC2) or a group represented by formula (EC3). With respect to the total amount of substance of the ethylenically unsaturated group represented by formula (EC2) and the group represented by formula (EC3), the proportion of the ethylenically unsaturated group represented by formula (EC2) is 50 mol %, and the proportion of the group represented by formula (EC3) is 50 mol %.

[0334]

[0335] B-1 is a resin having a main chain in which repeating units enclosed in brackets [ ] are randomly bonded.

[0336] The Mn and Mw of each resin are shown in Table 3 below.

[0337]

[0338] <Polymerization Initiator> The structural formula of the compound used as the polymerization initiator is shown below.

[0339]

[0340] <Crosslinking Agent> The structural formula of the compound used as the crosslinking agent is shown below.

[0341]

[0342] <Silane Coupling Agent> The structural formula of the compound used as the silane coupling agent is shown below.

[0343]

[0344] <Migration Inhibitor> The structural formula of the compound used as the migration inhibitor is shown below.

[0345]

[0346] <Base Generator> The structural formula of the compound used as the base generator is shown below.

[0347]

[0348] <Additives> The structural formulas of the compounds used as additives are shown below: H-1 is a light absorber, and I-1 is a polymerization inhibitor.

[0349]

[0350] <Solvent> The solvents used are as follows: DMSO: dimethyl sulfoxide GBL: γ-butyrolactone

[0351] <Evaluation> Evaluation was carried out as follows, and the results are shown in Tables 1 and 2 above.

[0352] [Resolution] Each resin composition was applied by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on the surface, and dried on a hot plate at 110°C for 3 minutes to form a resin composition layer (film) having a thickness of 5 μm after film formation. Subsequently, the film was exposed using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)). The exposure was performed through a mask in which a hole pattern with a diameter of 0.5 to 20 μm was formed at 1 μm intervals, at a wavelength of 365 nm and an exposure dose of 100 mJ / cm. ２ The resulting exposed film was heated on a hot plate at 120°C for 1 minute. The film was then developed for 15 seconds using cyclopentanone as a developer, rinsed for 30 seconds using PGMEA as a rinse, and heated at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C. After that, the film was heated at 230°C for 1 hour to produce a hole pattern. The diameter of the smallest size pattern among the hole patterns produced is shown in the "Resolution" column of Tables 1 and 2. The smaller the diameter of a hole pattern that can be formed, the better the resolution.

[0353] [Sensitivity] When a hole pattern was produced by changing the exposure dose in the hole pattern production method described in the evaluation method for [Resolution] above, the minimum exposure dose at which the film thickness of the pattern did not change before and after development was defined as the sensitivity. The sensitivity was 100 to 300 mJ / cm ２ The range is preferred.

[0354] [Film Residual Rate] Using the hole pattern preparation method described in the evaluation method for [Resolution] above, the ratio of the film thickness of the prepared pattern (after heating at 230°C for 1 hour) to the film thickness (5 µm) of the resin composition after film formation was defined as the film residual rate. That is, the film residual rate can be calculated by the following formula: Film residual rate = 100 x (film thickness of prepared pattern) / (film thickness of resin composition after film formation)

[0355] From the above results, it was found that the resin compositions of the examples of the present invention were excellent in resolution, and also had good sensitivity and film retention.

[0356] According to the present invention, it is possible to provide a resin composition having excellent resolution, a cured product obtained by curing the resin composition, a method for producing the cured product, a method for producing a laminate including the method for producing the cured product, and a method for producing a semiconductor device.

[0357] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2024-089094) filed on May 31, 2024, the contents of which are incorporated herein by reference.

Claims

1. A resin composition containing a resin having a repeating unit represented by the following formula (1-1) and having an ethylenically unsaturated group, and a polymerization initiator: In formula (1-1), X １ represents a tetravalent organic group, Y １ represents a divalent organic group. １ and Y １ At least one of the above includes at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). In formulas (2-1) to (2-4), * indicates the bonding position to other atoms.

2. The resin composition according to claim 1, wherein the resin has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-2), a repeating unit represented by the following formula (1-3), and a repeating unit represented by the following formula (1-4): In formula (1-2), A ２ is -O- or -NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ２ represents a hydrogen atom or a monovalent organic group; X ２ represents a tetravalent organic group, Y ２ represents a divalent organic group. ３ is -O- or -NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ３ represents a hydrogen atom or a monovalent organic group; X ３ represents a tetravalent organic group, Y ３ represents a divalent organic group. ４１ and A ４２ are each independently —O— or —NR Ｚ represents -, and R Ｚ represents a hydrogen atom or a monovalent organic group, R ４１ and R ４２ each independently represents a hydrogen atom or a monovalent organic group; X ４ represents a tetravalent organic group, Y ４ represents a divalent organic group.

3. The resin composition according to claim 2, wherein the imidization rate of said resin is 40% or more.

4. Y in the formula (1-1) １ The resin composition according to claim 1, comprising at least one selected from the group consisting of a group represented by the formula (2-1), a group represented by the formula (2-2), a group represented by the formula (2-3), and a group represented by the formula (2-4).

5. The resin composition according to claim 1, wherein the value of Qa defined by the following formula (a) is 0.1 or more and 2.0 or less. Formula (a) Qa = Q １ / Q ２ Q １ Q is the number of groups selected from the group consisting of the group represented by formula (2-1), the group represented by formula (2-2), the group represented by formula (2-3), and the group represented by formula (2-4) in one molecule of the resin. ２ is the number of ethylenically unsaturated bonds in one molecule of the resin.

6. Y in the formula (1-1) １ The resin composition according to claim 1, wherein the methyl group has an ethylenically unsaturated group.

7. The resin composition according to claim 1, further comprising a polymerizable compound.

8. The resin composition according to claim 1, further comprising a light absorber.

9. The resin composition according to claim 8, wherein the light absorber is at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds and coumarin compounds.

10. The resin composition according to claim 1, further comprising an organic solvent.

11. The resin composition according to claim 1, wherein the resin composition is a negative photosensitive resin composition.

12. The resin composition according to claim 1, which is used to form an interlayer insulating film for a rewiring layer.

13. A cured product obtained by curing the resin composition according to any one of claims 1 to 12.

14. A method for producing a cured product, comprising: a film-forming step of applying the resin composition according to any one of claims 1 to 12 onto a substrate to form a film; 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.

15. The method for producing a cured product according to claim 14, further comprising a heating step of heating the film at 50 to 450°C.

16. A method for producing a laminate, comprising the method for producing the cured product according to claim 14.

17. A method for manufacturing a semiconductor device, comprising the method for manufacturing the cured product according to claim 14.

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