WO2023276517A1

WO2023276517A1 - Resin composition, cured product, production method for cured product, electronic component, display device, and semiconductor device

Info

Publication number: WO2023276517A1
Application number: PCT/JP2022/021888
Authority: WO
Inventors: 荘司優; 小笠原央; 荒木斉
Original assignee: 東レ株式会社
Priority date: 2021-07-02
Filing date: 2022-05-30
Publication date: 2023-01-05
Also published as: TW202302710A; KR20240028331A; JPWO2023276517A1

Abstract

Provided are a resin composition that has a high breaking elongation and that has high crack resistance even after a thermal cycling test, a cured product obtained from said resin composition, and an electronic component, a display device, and a semiconductor device. This resin composition contains an (A) resin and a (B) resin, each of which has a specified structure at the ends thereof, said (A) resin and (B) resin containing at least one selected from the group consisting of a polyamide, a polyimide, a polybenzoxazole, precursors thereof, and copolymers thereof.

Description

Resin composition, cured product, method for producing cured product, electronic component, display device and semiconductor device

The present invention relates to a resin composition, a cured product, a method for producing a cured product, an electronic component, a display device, and a semiconductor device.

Conventionally, polyimide resins and polybenzoxazole resins, which are excellent in heat resistance and elongation at break, have been widely used for surface protective films and interlayer insulating films of semiconductor devices. Generally, polyimide and polybenzoxazole are obtained by thermally dehydrating and ring-closing a coating film of these precursors to obtain a thin film having excellent heat resistance and elongation at break. In that case, high-temperature firing at around 350° C. is usually required. However, for example, MRAM (Magnetoresistive Random Access Memory), which is promising as a next-generation memory, and sealing resin are vulnerable to high temperatures. Therefore, in order to be used as a surface protective film for such devices and an interlayer insulating film for a fan-out wafer level package in which a rewiring structure is formed on a sealing resin, it is cured by baking at a low temperature of about 250° C. or less, There is a demand for polyimide resins or polybenzoxazole resins that can provide properties comparable to those obtained by baking conventional materials at a high temperature of around 350°C.

When the resin composition is used for applications such as semiconductors, the film after heat curing remains as a permanent film inside the device, so the physical properties of the cured product, especially the elongation, are very important. Also, when used as an insulating film between wiring layers in a wafer level package, it is necessary that no cracks or peeling occur in a reliability test such as a thermal cycle test.

To solve these problems, a method using a polybenzoxazole precursor having an aliphatic group (Patent Document 1) or a photosensitive resin composition containing a novolac resin having a crosslinkable group has been proposed (Patent Document 2).

JP 2008-224984 A JP 2011-197362 A

However, the polybenzoxazole precursor having an aliphatic group described in Patent Document 1 and the cured product of the photosensitive resin composition containing the novolac resin described in Patent Document 2 are included in the cured product after the thermal cycle test. There is a problem that the resin deteriorates and cracks occur after the reliability test. In particular, since the novolak resin described in Patent Document 2 has a low breaking elongation when cured, cracks are likely to occur after a thermal cycle test.

In order to solve the above problems, the present invention relates to the following. That is, the resin composition of the present invention is a resin composition containing (A) a resin represented by formula (1) and (B) a resin represented by formula (2).

In formula (1), each X independently represents a repeating structural unit of polyamide, polyimide, polybenzoxazole or a precursor thereof, and R ¹ is a monovalent represented by formula (3) or formula (4). is the base. R ^a represents a group selected from the group consisting of R ¹ , a hydrogen atom, and a monovalent organic group having 1 to 20 carbon atoms. n ₁ is an integer from 2 to 200;

In formula (2), each Y independently represents a repeating structural unit of polyamide, polyimide, polybenzoxazole, or a precursor thereof, and ^R2 is a monovalent group represented by formula (5). R ^b represents a group selected from the group consisting of R ² , a hydrogen atom and a monovalent organic group having 1 to 20 carbon atoms. n2 is an integer from ₂ to 200;

In formula (3), * represents a bond.

In formula (4), R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. * represents a joint.

In formula (5), * represents a bond.

According to the present invention, it is possible to obtain a resin composition that has a high elongation at break and gives a cured product that has high crack resistance even after a thermal cycle test.

The present invention will be described in detail below.

The resin composition of the present invention comprises (A) a resin represented by formula (1) (hereinafter sometimes referred to as component (A) or (A) resin) and (B) represented by formula (2). containing a resin (hereinafter sometimes referred to as (B) component or (B) resin).

In formula (3), * represents a bond.

In formula (5), * represents a bond.

When the resin composition of the present invention contains component (A) and component (B), the terminal of component (A) reacts with the terminal of component (B) in low-temperature curing at 250° C. or less, resulting in a cured product. Since the molecular weight of the resin inside can be increased, the elongation at break and the crack resistance after the thermal cycle test are improved.

X in component (A) and Y in component (B) are each independently repeating structural units of polyamide, polyimide, polybenzoxazole, or precursors thereof. Polyimide is not particularly limited as long as it has an imide ring. The polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring upon dehydration and ring closure, and may contain polyamic acid, polyamic acid ester, or the like. The polyamide is not particularly limited as long as it has an amide bond. Polybenzoxazole is not particularly limited as long as it has a benzoxazole ring. The polybenzoxazole precursor is not particularly limited as long as it has a structure that becomes polybenzoxazole having a benzoxazole ring upon dehydration and ring closure, and may contain polyhydroxyamide or the like.

Components (A) and (B) are used because they can easily provide excellent properties as surface protective films for semiconductor devices, interlayer insulating films, insulating layers for display devices such as organic light-emitting devices, and flattening films for TFT substrates. It is preferable that the amount of outgas at a high temperature of 160° C. or higher after heat treatment is small. Specifically, component (A) and component (B) preferably contain at least one selected from the group consisting of polyamide, polyimide, polybenzoxazole, precursors thereof, and copolymers thereof.

The components (A) and (B) can be obtained, for example, by polycondensing dicarboxylic acids, dicarboxylic acid derivatives, acid dianhydrides, diamines, acid anhydrides, monoamines, and the like. Specific examples of dicarboxylic acid derivatives include, but are not limited to, dicarboxylic acid dichlorides, active amide compounds such as hydroxybenzotriazole and imidazole.

R ¹ in component (A) and R ² in component (B) contain monoamines, acid anhydrides, monocarboxylic acids, monocarboxylic acid chloride compounds, monoactive ester compounds, etc. as main chain end caps. Obtained by condensation. R ¹ in component (A) and R ² in component (B) are at least one hydrogen atom selected from maleimide, maleic acid monoalkyl ester, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, etc. , a structure in which the OH or amino group of the carboxyl group is removed (hereinafter sometimes referred to as "residue").

Furthermore, R ^a in components (A) and (B) represents a group selected from the group consisting of R ¹ , a hydrogen atom, and an organic group having 1 to 20 carbon atoms, and R ^b represents R ² , a hydrogen atom. , and a group selected from the group consisting of monovalent organic groups having 1 to 20 carbon atoms. Examples of organic groups having 1 to 20 carbon atoms 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-amino naphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy -5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4- Residues of monoamines such as aminothiophenol, residues of imides such as phthalimide, nadimide, hexahydrophthalimide, 3-hydroxyphthalimide, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythio Phenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto - Residues of monocarboxylic acids such as 5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, and terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6- Examples include, but are not limited to, residues of one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene.

Of X and Y in component (A) and component (B),
The repeating structural unit of the polyimide is a repeating structural unit represented by formula (6),
The repeating structural unit of the polyamide, polyimide precursor or polybenzoxazole precursor is a repeating structural unit represented by formula (7), and the repeating structural unit of the polybenzoxazole is represented by formula (8). is preferably a repeating structural unit.

In formula (6), R ⁴ represents a tetravalent organic group having 4 to 40 carbon atoms. R ⁵ represents a divalent organic group having 4 to 40 carbon atoms.

In formula (7), R ⁶ represents a divalent to octavalent organic group having 4 to 40 carbon atoms. R ⁷ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R ⁸ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. q and r are in the range of 0≤q≤4, 0≤r≤4 and represent integers satisfying 0≤q+r≤6. s represents an integer from 0 to 2;

In formula (8), R ⁹ represents a divalent organic group having 4 to 40 carbon atoms. R ¹⁰ represents a divalent organic group having 4 to 40 carbon atoms.

In formula (6), R ⁴ represents a tetravalent organic group having 4 to 40 carbon atoms. Examples of the tetravalent organic group having 4 to 40 carbon atoms include residues of aromatic tetracarboxylic acids and aliphatic tetracarboxylic acids. The aliphatic tetracarboxylic acid residue is preferably an alicyclic tetracarboxylic acid residue.

Specific examples of the residue of the aromatic tetracarboxylic acid include pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2 ,2′,3,3′-biphenyltetracarboxylic acid, 3,3′,4,4′-diphenylethertetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3 ,3′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(3,4 -dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3 ,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4 -dicarboxyphenoxy)phenyl}fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3, Examples include residues of 4,9,10-perylenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and the like.

Specific examples of the residue of the aliphatic tetracarboxylic acid include residues of cyclobutanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Among them, pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-diphenylethertetracarboxylic acid, 2,2-bis(3,4-di carboxyphenyl) is the residue of hexafluoropropane. Two or more types of these residues may be included.

In formula (7), R ⁶ represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and R ¹⁰ represents a divalent organic group having 4 to 40 carbon atoms in formula (8). Examples of divalent to octavalent organic groups having 4 to 40 carbon atoms include residues of aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids, aliphatic dicarboxylic acids, aliphatic tetracarboxylic acids, and the like. be done.

Examples of the aromatic dicarboxylic acid residue include residues of terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, and the like. be done.

Examples of the aromatic tricarboxylic acid residue include residues of trimellitic acid, trimesic acid, diphenylethertricarboxylic acid, biphenyltricarboxylic acid, and the like.

Examples of the aromatic tetracarboxylic acid residue include pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2, 2′,3,3′-biphenyltetracarboxylic acid, 3,3′,4,4′-diphenylethertetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3, 3′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(3,4- dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3, 4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4- dicarboxyphenoxy)phenyl}fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4 , 9,10-perylenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and the like.

Examples of residues of aliphatic dicarboxylic acids include residues of adipic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

Examples of aliphatic tetracarboxylic acids include residues of cyclobutanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.

R6 and ^R10 may contain ^two or more of these residues.

R ⁸ is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, such as a hydrocarbon group, a fluoroalkyl group, a phenyl group and a substituted phenyl group. Substituents of the substituted phenyl group include hydrocarbon groups, fluoroalkyl groups, phenyl groups, nitro groups, cyano groups, carboxyl groups, hydroxyl groups, amino groups, sulfonic acid groups and the like.

R ⁵ in formula (6), R ⁷ in formula (7), and R ⁹ in formula (8) contain structures derived from diamine residues. Specific examples of the diamine residue include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,4-bis( 4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-amino phenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3 ,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2′,3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3′,4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl, 9,9-bis(4-amino Phenyl)fluorene residues, residues of compounds in which at least part of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, residues of aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the following and the residues of the structures shown in . R ⁵ , R ⁷ and R ⁹ may contain two or more of these residues.

* represents a joint.

* represents a joint.

R ⁴ in formula (6) and R ⁶ in formula (7) are structures represented by formula (9), and R ⁵ in formula (6) and R ⁷ in formula (7) are It preferably has a structure represented by formula (10).

In formula (9), R ¹¹ represents a single bond, —O—, —C(CF ₃ ) ₂ —, or a structure represented by formula (11). * represents a joint.

In formula (10), R ¹² is a single bond, —O—, —C(CH ₃ ) ₂ — or —C(CF ₃ ) ₂ —, and each R ¹³ is independently a hydrogen atom or a represents a monovalent organic group of ∼20. t and u each independently represent an integer of 0 to 4 and satisfy t+u=4. * represents a joint.

In formula (11), R ¹⁴ represents a structure represented by a single bond, —O—, —C(CH ₃ ) ₂ — or —C(CF ₃ ) ₂ —. * represents a joint.

The resin composition contains (A) component and (B) component having the structural units of the formula (9) and the formula (10) in the formula (6) or (7). High breaking elongation and high crack resistance can be easily obtained in cured products.

As a specific example of the formula (9), it is preferable to have the structural units shown below.

* represents a joint.

As a specific example of the formula (10), it is preferable to have the structure shown below.

* represents a joint.

R ⁹ in formula (8) is a structure represented by a single bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, or a fluoroalkylene group having 1 to 6 carbon atoms, and R ¹⁰ is represented by formula (12 ) preferably has a structure represented by

In formula (12), R ¹⁵ represents a structure represented by a single bond, —O—, —C(CH ₃ ) ₂ — or —C(CF ₃ ) ₂ —. * represents a chemical bond.

By containing the (A) component and (B) component having these structural units in the resin composition, it becomes easier to obtain high elongation and high crack resistance in the cured product of the resin composition.

It was noted that R ¹ and R ² in the resin composition of the present invention have properties as an electron donor and an electron acceptor, respectively, and tend to form a charge transfer complex with each other. Therefore, the coexistence of R ¹ and R ² significantly improves the reactivity between the terminal groups compared to the presence of R ¹ or R ² alone.

At the terminal reaction growth active sites, due to electronic interaction, the growth active sites of ^R1 tend to react selectively with ^R2 , and the growth active sites of ^R2 with ^R1 tend to form alternating copolymers. Therefore, when the ratio of the amount of terminal group R ¹ of component (A) to the amount of terminal R ² of component (B) in the resin composition of the present invention is M (details of the calculation method will be described later), , the terminal group R ¹ of the component (A) when the total integral value of the signals derived from the hydrogen atoms of the amide bonds appearing at 9 to 11 ppm in the ¹ H-NMR spectrum of the components (A) and (B) is taken as 100 M is defined as M = 3r ₁ / 2r ₂ , where r _{2 is the total integral value of the signal derived from the hydrogen atom of the component (B) and r 2} _is the total integral value of the signal derived from the hydrogen atom of the terminal group R ² of the component (B) is preferably 0.25 or more and 4 or less, more preferably 0.7 or more and 2 or less. When M is within the above range, it becomes easier to form a charge transfer complex of R ¹ and R ² , and the reactivity between the terminal groups is significantly improved, so that the cured product has high elongation at break and high crack resistance. can get things. When M is 0.25 or more and 4 or less, a cured product having sufficient mechanical strength can be obtained, and the cured product has high breaking elongation and high crack resistance.

The ratio M of the substance amount of terminal group R ¹ of component (A) to the substance amount of terminal R ² of component (B) can be determined by nuclear magnetic resonance (1H-NMR, 13C-NMR), infrared absorption spectroscopy (IR method), matrix-assisted laser desorption ionization method-time-of-flight mass spectrometry (MALDI-TOFMS) in a resin composition in which the molecular structures of components (A) and (B) have been identified, 1H-NMR. use.

In the obtained ¹ H-NMR spectrum, the signal originating from the R ¹ hydrogen atom appears at 5 to 6 ppm and the signal originating from the R ² hydrogen atom appears at 6 to 6.5 ppm. When the total integrated value of the signal derived from the hydrogen atom of the amide bond appearing at 9 to 11 ppm is 100, the total integrated value of the signal derived from the hydrogen atom of the terminal group R ¹ of the component (A) is r ₁ and the component (B) The total integral value of the signal derived from the hydrogen atom of the terminal group R ² of is r ₂ , and the material amount ratio M between the terminal group R ¹ of the component (A) and the terminal R ² of the component (B) in the resin composition is It can be calculated as M=3r ₁ /2r ₂ .

The weight average molecular weight of the resin composition of the present invention is preferably 5,000 or more and 35,000 or less. A weight-average molecular weight of 5,000 or more in terms of polystyrene by GPC (gel permeation chromatography) is preferable because cracks do not occur in the film-forming process before curing, and 10,000 or more is more preferable. On the other hand, by setting the weight average molecular weight to 35,000 or less, the reaction efficiency between the ends can be improved, and the breaking elongation of the cured product is improved. In order to obtain a higher elongation at break, the weight average molecular weight is more preferably 30,000 or less, even more preferably 25,000 or less.

The weight average molecular weight (Mw) can be confirmed using GPC (gel permeation chromatography). For example, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is measured as a developing solvent and can be obtained in terms of polystyrene.

The resin composition of the present invention may contain a photoacid generator. Photosensitivity can be imparted to the resin composition by containing a photoacid generator.
The photoacid generator generates acid in the light-irradiated portion of the resin composition. As a result, the solubility of the light-irradiated portion in an alkaline developer increases, so that a positive pattern in which the light-irradiated portion dissolves can be obtained.

The photoacid generators mentioned above include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like. The resin composition of the present invention can further contain a sensitizer and the like, if necessary.

As the quinonediazide compound, a compound in which a sulfonic acid of naphthoquinonediazide is ester-bonded to a compound having a phenolic hydroxyl group is preferable.

Compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP -IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DMLMBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML- HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), 2 ,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol compounds such as E, methylenebisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

Sulfonic acids of naphthoquinonediazide include 4-naphthoquinonediazide sulfonic acid and 5-naphthoquinonediazide sulfonic acid.

In addition, it is preferable that 50 mol% or more of all the functional groups of the compound having a phenolic hydroxyl group are substituted with quinonediazide. By using a quinonediazide compound substituted by 50 mol % or more, the affinity of the quinonediazide compound for an alkaline aqueous solution is lowered. As a result, the solubility of the resin composition in the unexposed area in an alkaline aqueous solution is greatly reduced. Furthermore, the quinonediazide sulfonyl group is converted to indenecarboxylic acid by exposure, and a high dissolution rate in an alkaline aqueous solution of the resin composition having photosensitivity in the exposed area can be obtained. That is, as a result, the dissolution rate ratio between the exposed area and the unexposed area of the composition can be increased, and a pattern with high resolution can be obtained.

By containing such a quinonediazide compound, a resin composition having positive-type photosensitivity that is sensitive to the i-line (365 nm), h-line (405 nm), g-line (436 nm) of a general mercury lamp and broadband including them. can get things. Further, the photoacid generator may be contained alone or in combination of two or more, and a resin composition having high sensitivity and photosensitivity can be obtained.

As the quinonediazide, both a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group are preferably used. A 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength exposure. A 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. It is preferable to select a 4-naphthoquinonediazide sulfonyl ester compound or a 5-naphthoquinone diazidesulfonyl ester compound depending on the wavelength of exposure.

It is also possible to obtain a naphthoquinonediazidesulfonyl ester compound containing a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the same molecule. A 4-naphthoquinonediazide sulfonyl ester compound and a 5-naphthoquinone diazidesulfonyl ester compound can also be used in combination. A quinonediazide compound can be synthesized by a known method through an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid compound. By using a quinonediazide compound, the resolution, sensitivity, and film retention rate are further improved.

Among the photoacid generators, sulfonium salts, phosphonium salts and diazonium salts are preferable because they moderately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferred.

The content of the photoacid generator is preferably 0.1 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass as the total amount of the components (A) and (B). When the content of the photoacid generator is 0.1 parts by mass or more and 100 parts by mass or less, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance, and breaking elongation of the film after heat treatment. .

When the photoacid generator contains a quinonediazide compound, the content of the photoacid generator is more preferably 1 part by mass or more, and 3 parts by mass, relative to 100 parts by mass of the total amount of components (A) and (B). The above is more preferable. Moreover, 100 mass parts or less are more preferable, and 80 mass parts or less are still more preferable. When the amount is 1 part by mass or more and 100 parts by mass or less, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and breaking elongation of the film after heat treatment.

When the photoacid generator contains a sulfonium salt, phosphonium salt or diazonium salt, the content of the photoacid generator is 0.1 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B). The above is more preferable, 1 part by mass or more is more preferable, and 3 parts by mass or more is particularly preferable. Moreover, it is more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less. When the amount is 0.1 parts by mass or more and 100 parts by mass or less, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and breaking elongation of the film after heat treatment.

The resin composition of the present invention preferably contains a photopolymerization initiator and a photopolymerizable compound.

The photopolymerization initiator and photopolymerizable compound polymerize in the light-irradiated portion of the resin composition and become insoluble in the developer. As a result, the solubility in the developing solution of the light-irradiated portion is drastically reduced, so that a negative pattern in which the light-unirradiated portion dissolves can be obtained.

The following are examples of photopolymerization initiators.

Benzophenones such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone. benzylidenes such as 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone and 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone; 7-diethylamino-3-thenonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylbenzimidazolyl)coumarin, 3 - Coumarins such as (2-benzothiazolyl)-7-diethylaminocoumarin. anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone and 1,2-benzanthraquinone; benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; mercaptos such as ethylene glycol di(3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; glycines such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine, N-(4-cyanophenyl)glycine; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o(methoxycarbonyl)oxime, 1-phenyl-1,2-propane dione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, bis(A-isonitrosopropiophenone oxime) isophthal, 1,2-octane Dione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), OXE02 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), NCI-831 (trade name, manufactured by ADEKA Corporation), etc. Oximes: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one A-aminoalkylphenones such as 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole and the like.

Of these, the above oximes are preferred. More preferred are 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, bis(A -isonitrosopropiophenone oxime) isophthal, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), OXE02, NCI-831. These are used alone or in combination of two or more. The structures of OXE-02 and NCI-831 are shown in the following formulas.

Among these, the above benzophenones, glycines, mercaptos, oximes, A-aminoalkylphenones, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl A combination selected from biimidazoles is preferred in terms of photoreactivity.

The content of the photopolymerization initiator is preferably 0.1 to 60 parts by mass, more preferably 0.2 to 40 parts by mass with respect to 100 parts by mass as the total amount of components (A) and (B). When the amount is 0.1 part by mass or more, sufficient radicals are generated by light irradiation, and sensitivity is improved. The solubility in the developer is improved.

Examples of the photopolymerizable compound include compounds having unsaturated double bond-containing groups such as vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups, and unsaturated triple bond-containing groups such as propargyl groups. The photopolymerizable compound may contain two or more of these unsaturated bond-containing groups. Among these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred from the standpoint of polymerizability. Moreover, the number of unsaturated bonds in the photopolymerizable compound is preferably 1 to 6 from the viewpoint of suppressing cracks in the cured product caused by excessive cross-linking points due to the polymerization reaction.

Examples of photopolymerizable compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2- vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, Neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate , 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-diacryloyloxy-2-hydroxypropane, 1,3-dimethacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N -methylolacrylamide, 2,2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl Nil methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethyl Len oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A dimethacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, propoxylated ethoxylated bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam etc. can be contained. The photopolymerizable compound may contain two or more of these.

Among these, photopolymerizable compounds include 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol tri Acrylates, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, 2,2,6 ,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N-methyl-2, 2,6,6-tetramethylpiperidinyl acrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, propylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A methacrylate, propoxylated ethoxylated bisphenol A diacrylate , propoxylated ethoxylated bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam. Among them, it is more preferable to contain dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified bisphenol A diacrylate, ethylene oxide-modified bisphenol A dimethacrylate, propylene oxide-modified bisphenol A diacrylate, and propylene oxide-modified bisphenol A dimethacrylate. .

The content of the photopolymerizable compound in the resin composition of the present invention is 40 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B) from the viewpoint of improving the residual film rate after development. It is preferably 50 parts by mass or more, more preferably 50 parts by mass or more. On the other hand, from the viewpoint of improving the breaking elongation of the cured product, the content of the photopolymerizable compound is 150 parts by mass or less with respect to 100 parts by mass of the total amount of components (A) and (B). is preferred, and 100 parts by mass or less is more preferred.

The resin composition of the present invention may contain a thermal cross-linking agent. In the present invention, the thermal cross-linking agent includes at least two groups selected from the group consisting of acrylic groups, methacrylic groups, epoxy groups, oxetanyl groups, benzoxazine structures, alkoxymethyl groups and methylol groups. is a compound. Thermal cross-linking agents preferably include, but are not limited to, compounds having at least two alkoxymethyl or methylol groups. Here, "having at least two alkoxymethyl groups or methylol groups" means having two or more alkoxymethyl groups, having two or more methylol groups, and having a total of two or more alkoxymethyl groups and methylol groups. Represents either By having at least two of these groups, a crosslinked structure can be formed by a condensation reaction with a resin and a molecule of the same kind. When used in combination with a photoacid generator, a wider range of designs is possible for improving sensitivity and breaking elongation of cured products.

Preferred examples of thermal cross-linking agents include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP and DML-PSBP. , DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML -P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM -BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC (registered trademark)" MX-290, NIKALAC MX -280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.). You may contain 2 or more types of these. Among these, when HMOM-TPHAP and MW-100LM are contained, reflow hardly occurs during curing and the pattern becomes highly rectangular, which is more preferable.

The content of the compound having at least two alkoxymethyl groups or methylol groups is preferably 10 parts by mass or less with respect to 100 parts by mass as the total amount of components (A) and (B). Within this range, a wide range of designs can be made more appropriately for improving the sensitivity and breaking elongation of the cured product.

The resin composition of the present invention preferably contains (G) a compound represented by formula (13) (hereinafter sometimes referred to as component (G)). These compounds have a structure that does not have an aromatic ring in the molecule, so that the solubility in an alkaline developer increases, and patterning can be performed with high sensitivity. Furthermore, the decomposition of (G) in the resin cured product due to heat or light irradiation including ultraviolet rays can be suppressed, and three-dimensional cross-linking can be formed, so it has a high breaking elongation and high crack resistance even after a thermal cycle test. It is possible to obtain a cured product having.

(In formula (13), L ¹ represents a structure represented by an alkylene group having 1 to 8 carbon atoms.)
(G) Compounds represented by formula (13) include, for example, “TEPIC (registered trademark)”-S, “TEPIC”-L, “TEPIC”-VL, and “TEPIC”-FL. From the viewpoint of compatibility and curability, it is preferable to use these compounds. A product name (manufactured by Shikoku Kasei Co., Ltd.) may also be used.

(G) The content of the compound represented by formula (13) is 5 parts by mass or more with respect to 100 parts by mass of the total amount of components (A) and (B) from the viewpoint of improving crack resistance in thermal cycles. preferably 10 parts by mass or more. In addition, from the viewpoint of ease of handling and lack of tackiness on the surface of the film when formed into a film, the total amount of component (A) and component (B) may be 100 parts by mass or less with respect to 100 parts by mass. preferable.

The resin composition of the present invention may contain an adhesion improver. Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group-containing A compound obtained by reacting a silicon compound can be contained. You may contain 2 or more types of these.

By containing an adhesion improver, adhesion to an underlying base material such as a silicon wafer, ITO, SiO ₂ , or silicon nitride can be enhanced when developing a resin film. In addition, resistance to oxygen plasma and UV ozone treatment used for cleaning can be enhanced.

The content of the adhesion improver in the resin composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass as the total amount of components (A) and (B). By setting it as such a range, the adhesiveness after image development is high, and the resin composition excellent in resistance to oxygen plasma and UV ozone treatment can be provided.

The resin composition of the present invention may contain a compound having a phenolic hydroxyl group in order to facilitate alkali developability. Since the resin composition contains a compound having a phenolic hydroxyl group, it is almost insoluble in an alkaline developer before exposure, and easily dissolved in an alkaline developer after exposure. Easier to develop in time. Therefore, it becomes easier to improve the sensitivity.

Compounds having a phenolic hydroxyl group selected from these points include, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP -MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisPHAP , TrisPPA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC , Bis236T-OCHP, methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2 ,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol and the like. The compound having a phenolic hydroxyl group may contain two or more of these.

The resin composition of the present invention may contain a surfactant as necessary. By containing a surfactant, it is possible to improve the wettability with the substrate and improve the film thickness uniformity of the coating film. Commercially available compounds can be used as surfactants. Specifically, the silicone-based surfactants include the SH series, SD series, and ST series of Toray Dow Corning Silicone Co., Ltd., the BYK series of BYK Chemie Japan, the KP series of Shin-Etsu Silicone Co., Ltd., the Disform series of NOF Corporation, Toshiba Silicone Co., Ltd.'s TSF series, etc., and fluorine-based surfactants include Dainippon Ink Industry's "Megafac (registered trademark)" series, Sumitomo 3M's Florard series, and Asahi Glass' "Surflon (registered trademark)" series. Trademark)" series, "Asahi Guard (registered trademark)" series, EF series of Shin-Akita Kasei Co., Ltd., Polyfox series of Omnova Solution Co., Ltd., and the like. Surfactants obtained from acrylic and/or methacrylic polymers include, but are not limited to, Polyflow series from Kyoeisha Chemical Co., Ltd., and "Disparon (registered trademark)" series from Kusumoto Kasei Co., Ltd.

The content of the surfactant is preferably 0.001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass as the total amount of components (A) and (B). Within the above range, the wettability between the resin composition and the substrate and the film thickness uniformity of the coating film can be improved without causing defects such as air bubbles and pinholes.

The resin composition of the present invention may contain a solvent. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyamide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene ethers such as glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. You may contain 2 or more types of these.

The content of the solvent is preferably 100 parts by mass or more for the total amount of 100 parts by mass of the components (A) and (B), since the composition is easily dissolved. It is preferable to contain 1,500 parts by mass or less because it is easy to form.

Next, a method for producing the resin composition of the present invention will be described. For example, the components (A) and (B) are mixed with, if necessary, a photoacid generator, a photopolymerization initiator, a thermal cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, a surfactant, a solvent, and the like. The resin composition can be obtained by dissolving the resin composition.

Dissolution methods include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 25°C to 80°C. In addition, the order of dissolving each component is not particularly limited, and for example, a method of dissolving compounds in order of low solubility can be mentioned. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. Even when the mixture is stirred, it may be heated as necessary, and the temperature is usually 25°C to 80°C. In addition, for ingredients that tend to generate air bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, dissolving the other ingredients before adding them at the end will prevent poor dissolution of other ingredients due to air bubbles. can be prevented.

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa·s at 25°C. A desired film thickness can be easily obtained by adjusting the solid content concentration so that the viscosity is 2 mPa·s or more. On the other hand, if the viscosity is 5,000 mPa·s or less, it becomes easy to obtain a highly uniform coating film. The viscosity measurement here is a measurement using a TVE-25 type viscometer (manufactured by Toki Sangyo Co., Ltd.), a former E-type viscometer/DVE-type viscometer, and 1.1 mL of the resin composition of the present invention is sampled. and pour into the sample cup. Depending on the viscosity, torque is selected in the range of 65-6000 μN·m and measured in the range of rotational speeds of 0.5-100 rpm. The resin composition of the present invention having such a viscosity can easily be obtained by adjusting the combined content of component (A) and component (B) in 100% by mass of the resin composition of the present invention to 5 to 60% by mass. can get to Here, solid content concentration refers to components other than the solvent.

The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, and 0.02 μm. Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred.

The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. In the curing reaction, cross-linking reaction and ring closure reaction proceed by heat, light, etc., and the obtained cured product has improved heat resistance, elongation at break and chemical resistance. When the cured product is heat treated for 5 minutes to 2 hours between 50 ° C. and 200 ° C. where the solvent in the resin composition before curing volatilizes, the cured product film after heat treatment is compared to the cured product film thickness before heat treatment. If the film thickness change rate is within 10%, it is assumed that the film is cured. The cured product of the present invention has high elongation at break and high crack resistance even after a thermal cycle test, and can improve the reliability of the semiconductor device, electronic component, and display device of the present invention.

The cured product of the present invention contains a resin having a structure represented by formula (14) or (15). These structures are structures in which R ¹ of component (A) and R ² of component (B) in the resin composition of the present invention react after heat curing, and when the cured product contains a resin having these structures A cured product having high elongation at break and high crack resistance can be obtained due to the extension of the polymer chain due to the reaction between the polymer ends. When R ¹ of component (A) and R ² of component (B) in the resin composition of the present invention react after heat curing, they have a structure represented by formula (14) or formula (15) due to their bonding mode. It will be. Therefore, the cured product of the present invention may have only the structure represented by formula (14), may have only the structure represented by formula (15), or may have formula (14) You may have the structure represented by the formula (15) and the structure represented by the formula (15) at the same time. These structures in the cured product are obtained by hydrolyzing the cured product with an alkali or the like, or the cured product itself, by nuclear magnetic resonance spectroscopy (1H-NMR, 13C-NMR), It can be identified using infrared absorption spectroscopy (IR method), matrix-assisted laser desorption/ionization method-time-of-flight mass spectrometry (MALDI-TOFMS), and the like.

* represents a chemical bond.

The cured product of the present invention preferably contains a resin having a trifluoromethyl group. Having a trifluoromethyl group improves the hydrophobicity of the cured product and improves the crack resistance in a thermal cycle test. The cured product may contain a resin having a structure represented by formula (14) or formula (15) and a trifluoromethyl group. Moreover, the cured product may contain a resin that does not have the structure represented by the formula (14) or (15) and has a trifluoromethyl group. From the viewpoint of compatibility, the cured product preferably contains a resin having a structure represented by formula (14) or formula (15) and a trifluoromethyl group.

The method for producing the cured product of the present invention will be explained.

The method for producing a cured product of the present invention includes a step of applying the resin composition of the present invention, a step of forming a pattern through an ultraviolet irradiation step and a developing step, and a step of heating to form a relief pattern layer of the cured product. is preferably included.

Hereinafter, the term "resin film" refers to a film obtained by coating the resin composition of the present invention on a substrate and drying it.

First, in the step of applying the resin composition of the present invention, the resin composition of the present invention is applied onto a substrate and dried to obtain a resin film. As the resin composition of the present invention, it is preferable to use a resin composition containing the above photoacid generator, or a resin composition containing the above photopolymerization initiator and a photopolymerizable compound. Drying is preferably carried out using an oven, hot plate, infrared rays, or the like, at a temperature of 50° C. to 140° C. for 1 minute to 2 hours. Examples of substrates include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and circuit-forming materials disposed on these substrates, but are not limited to these. Examples of coating methods include a spin coating method, a slit coating method, a dip coating method, a spray coating method, and a printing method. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating is usually applied so that the film thickness after drying is 0.1 to 150 μm.

Prior to application, the base material to be coated with the resin composition may be pretreated with the above-described adhesion improver. For example, a solution obtained by dissolving 0.5 to 20 parts by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate is used. Examples thereof include methods of treating the surface of the base material by spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like. After treating the surface of the base material, it may be dried under reduced pressure, if necessary. Further, after that, a heat treatment at 50° C. to 280° C. may be performed to advance the reaction between the substrate and the adhesion improver.

The process of forming a pattern through an ultraviolet irradiation process and a development process may include an exposure process of irradiating chemical warfare through a mask having a desired pattern on a photosensitive resin film. Chemical warfare used for exposure includes ultraviolet rays, visible rays, electron beams, X-rays, and the like. is preferably used.

Then, the exposed resin film is developed. Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, Aqueous solutions of alkaline compounds such as dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone , polar solvents such as dimethylacrylamide, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone. Solvents include, but are not limited to. The developer may be a mixed solution of two or more selected from the above solvents. After development, the film can be rinsed with water, ethanol, alcohol such as isopropyl alcohol, ethyl lactate, ester such as propylene glycol monomethyl ether acetate, but not limited thereto. The solution used for the rinse treatment may be a mixed solution of two or more selected from the above solvents.

Next, in the step of heating to form a relief pattern layer of the cured product, the relief pattern layer of the cured product is formed by heat-treating the resin film to promote thermal cross-linking reaction and thermal ring-closing reaction.

The heat treatment of the resin film may be performed by gradually increasing the temperature, or may be performed while continuously increasing the temperature. The heat treatment is preferably carried out for 5 minutes to 5 hours. As an example, heat treatment is performed at 140° C. for 30 minutes, followed by heat treatment at 320° C. for 60 minutes. The heat treatment temperature is preferably 140° C. or higher and 400° C. or lower. The heat treatment temperature is preferably 140° C. or higher, more preferably 160° C. or higher, in order to advance the thermal crosslinking reaction and the thermal ring-closing reaction. The heat treatment temperature is preferably 400° C. or lower, more preferably 350° C. or lower, in order to provide an excellent cured product and improve the yield.

The electronic component, display device or semiconductor device of the present invention comprises the cured product of the present invention. By having the cured product of the present invention, it is possible to obtain a highly reliable electronic component, display device or semiconductor device that does not generate cracks even after a thermal cycle test. Examples of the configuration of the electronic component, display device, or semiconductor device of the present invention include, for example, the electronic component, display device, or semiconductor device described in JP-A-2020-66651 and WO 2021/085321. is not limited to

The present invention will be described below with reference to examples, etc., but the present invention is not limited to these examples. The resin compositions in the examples were evaluated by the following methods. For the evaluation, a resin composition (hereinafter referred to as varnish) filtered in advance through a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Calculation of substance amount ratio M between terminal group R ¹ of component (A) and terminal R ² of component (B) Terminal group R ¹ of component (A) and terminal R of component (B) in the resin composition ² was calculated using 1H-NMR. The measurement conditions are as follows.
Measuring equipment: JNM-ECZ400R manufactured by JEOL RESONANCE
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)
Measurement temperature: 40°C
In the obtained ¹ H-NMR spectrum, the signal originating from the R ¹ hydrogen atom appears at 5 to 6 ppm and the signal originating from the R ² hydrogen atom appears at 6 to 6.5 ppm. When the total integrated value of the signal derived from the hydrogen atom of the amide bond appearing at 9 to 11 ppm is 100, the total integrated value of the signal derived from the hydrogen atom of the terminal group R ¹ of the component (A) is r ₁ and the component (B) The total integral value of the signal derived from the hydrogen atom of the terminal group R ² of is r ₂ , and the material amount ratio M between the terminal group R ¹ of the component (A) and the terminal R ² of the component (B) in the resin composition is Calculated as M=3r ₁ /2r ₂ .

(2) Measurement of molecular weight The weight-average molecular weight of the resin composition was obtained by standard polystyrene conversion using gel permeation chromatography (GPC).

Specifically, the weight average molecular weight was measured using the following apparatus and conditions.
Measuring device: Alliance e2695 manufactured by System Waters
Detector: 2489 UV/Vis Detector (measurement wavelength 260 nm)
Measurement conditions: column TOSOH TSK Guard column
TOSOH TSK-GEL α-4000
TOSOH TSK-GEL α-2500
Developing solution: NMP (containing 0.05 M lithium chloride and 0.05 M phosphoric acid)
Flow rate: 0.4 ml/min, detector: UV270 nm
If necessary, the resin composition may be diluted with a solvent (NMP (containing 0.05 M lithium chloride and 0.05 M phosphoric acid)) for measurement so that detection can be performed with an analyzable peak intensity.

(3) Breaking elongation evaluation A varnish is applied to an 8-inch silicon wafer by a spin coating method using a coating and developing device ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm and prebaked. After that, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 250° C. at 3.5° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 250° C. for 1 hour. rice field. When the temperature became 50° C. or lower, the wafer was taken out and immersed in 45 mass % hydrofluoric acid for 1 minute to peel off the cured product from the wafer. This film was cut into strips with a width of 1.5 cm and a length of 5 cm. The elongation at break was measured by pulling at 5 mm/min. Measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results. A value of breaking elongation of 40% or more was rated as very good (3), a value of 20% or more and less than 40% was rated as good (2), and a value of less than 20% was rated as poor (1).

(4) Evaluation of Crack Resistance The following evaluation substrates were prepared for evaluation of peeling on copper wiring. On an 8-inch silicon wafer, cylindrical copper wirings with a thickness of 5 μm and a diameter of 90 μm were formed at equal intervals so that the center-to-center distance of the copper wirings was 150 μm. This was used as an evaluation substrate.

The varnish was applied on the evaluation substrate by a spin coating method using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.) so that the film thickness after heat treatment at 120° C. for 3 minutes would be 8 to 12 μm. Pre-baking was performed to produce a resin film. All pre-baking was performed at 120° C. for 3 minutes.

After that, the resin film was heated from 50° C. to 250° C. at a rate of 3.5° C./min under a nitrogen stream using an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.). After heating, heat treatment was performed at 250° C. for 1 hour to cure the resin film and obtain a cured product. The film thickness after pre-baking is measured using a light interference film thickness measuring device Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. with a refractive index of 1.629. Measured at a refractive index of 1.773.

When the temperature reached 50°C or less, the evaluation substrate (hereinafter referred to as the sample) was taken out.

Next, the sample was put into a thermal cycle tester (conditions: -65°C/30min to 150°C/30min) and subjected to 200 cycles. After that, the sample was taken out and the presence or absence of cracks in the cured product was observed using an optical microscope. A total of 10 observations were made at 2 locations each at the center of the substrate and 4 edges of the substrate, with 0 cracks being evaluated as very good, 1-2 cracks being evaluated as good, and 3 or more cracks being generated. A sample with 4 cracks was rated as 2 as slightly defective, and a sample with 5 to 10 cracks was rated as 1 as defective. A smaller number of cracks indicates better crack resistance. The evaluation result is preferably 3 or 4, most preferably 4.

(5) Structural analysis of resin in cured product For the non-photosensitive varnishes of Examples 1 to 16, 21 to 24, and Comparative Examples 1 to 4, after prebaking on an 8-inch silicon wafer at 120 ° C. for 3 minutes After coating and pre-baking by a spin coating method using a coating and developing apparatus ACT-8 so that the film thickness of 11 μm, an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) was used to reduce the oxygen concentration. The temperature was raised to 250° C. at 3.5° C./min at 20 ppm or less, and heat treatment was performed at 250° C. for 1 hour. When the temperature became 50° C. or lower, the wafer was taken out and immersed in 45 mass % hydrofluoric acid for 1 minute to peel off the cured product from the wafer.

The photosensitive varnishes of Examples 17 to 20 were applied onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 so that the film thickness after prebaking at 120° C. for 3 minutes was 12 μm. After coating and pre-baking, exposure machine i-line stepper (manufactured by Nikon Corporation, NSR-2005i9C) was used with a mask capable of forming a circular opening pattern of 3 to 50 μm on the cylindrical copper wiring. It was exposed with an exposure dose of cm ² . After exposure, the film was developed using a 2.38% by mass tetramethylammonium (TMAH) aqueous solution (manufactured by Tama Kagaku Kogyo), rinsed with pure water, shaken off and dried to obtain a relief pattern film. After that, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 250° C. at an oxygen concentration of 20 ppm or less at 3.5° C./min, and heat treatment was performed at 250° C. for 1 hour. . When the temperature became 50° C. or lower, the wafer was taken out and immersed in 45 mass % hydrofluoric acid for 1 minute to peel off the cured product from the wafer.

2.0 g of the cured product thus obtained, 200 g of deionized water and 10 g of NaOH were added and stirred at 60°C for 8 hours. Subsequently, this solution was cooled to room temperature, 700 ml of ion-exchanged water was added, and the mixture was stirred for 30 minutes.

Next, a diluted HCl aqueous solution was prepared by diluting 20 g of concentrated hydrochloric acid (35% HCl aqueous solution) with 400 ml of deionized water.

The diluted HCl aqueous solution was gradually added to neutralize the alkaline hydrolysis aqueous solution. A precipitate generated after the neutralization was collected by filtration, and the separated precipitate was washed with about 850 ml of ion-exchanged water. The precipitate after washing was put into a hot air dryer and dried at 80° C. for 24 hours.

The precipitate obtained after drying was subjected to structural analysis of the cured product using 1H-NMR and FT-IR. The measurement conditions are as follows.
Measurement: 1H-NMR
Measuring equipment: JNM-ECZ400R manufactured by JEOL RESONANCE
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)
Measurement temperature: 40°C.
Measurement: FT-IR
Measuring equipment: INVENIO S manufactured by BRUKER
Mode: Transmission Specimen: KBr plate Accumulation times: 16
In the obtained 1H-NMR spectrum, the structure of formula (14) or formula (15) can be calculated from the integral ratio of each hydrogen atom, and in the obtained FT-IR spectrum, the structure of formula (14) or formula (15) Since a characteristic peak derived from a carbonyl group appears, the chemical structure of formula (14) or formula (15) can be identified. In particular, a characteristic signal derived from a hydrogen atom directly connected to the tertiary carbon of Formula (14) or Formula (15) appears at 2 to 4 ppm. A cured product in which the signal was observed was evaluated as 1, and a cured product in which the signal was not observed was evaluated as 0.

<Synthesis Example 1 Synthesis of Polyimide Precursor (A-1)>
Under a stream of dry nitrogen, 4.96 g (0.016 mol) of 4,4′-oxydiphthalic anhydride (hereinafter referred to as ODPA) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 2.16 g (0.02 mol) of p-phenylenediamine (hereinafter referred to as PDA) was added together with 25 g of NMP, reacted at 20° C. for 1 hour, and then reacted at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 2 Synthesis of Polyimide Precursor (A-2)>
Under a dry nitrogen stream, 4.96 g (0.016 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 4.00 g (0.02 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as DAE) was added together with 25 g of NMP, and reacted at 20°C for 1 hour and then at 50°C for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 3 Synthesis of Polyimide Precursor (A-3)>
Under a dry nitrogen stream, 4.96 g (0.016 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 6.40 g (0.02 mol) of 2,2'-bis(trifluoromethyl)benzidine (hereinafter referred to as TFMB) was added together with 25 g of NMP, reacted at 20°C for 1 hour, and then at 50°C for 2 hours. reacted. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 4 Synthesis of Polyimide Precursor (A-4)>
Under a dry nitrogen stream, 4.96 g (0.016 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 6.69 g (0.02 mol) of 2,2'-bis(4-aminophenyl)hexafluoropropane (hereinafter referred to as BIS-A-AF) was added together with 25 g of NMP, and reacted at 20°C for 1 hour. and then reacted at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 5 Synthesis of Polyimide Precursor (A-5)>
Under a dry nitrogen stream, 4.96 g (0.016 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 5.17 g (0.02 mol) of 2,2'-bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as BAP) was added together with 25 g of NMP, reacted at 20°C for 1 hour, and then The reaction was carried out at 50°C for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 6 Synthesis of Polyimide Precursor (A-6)>
Under a dry nitrogen stream, 4.96 g (0.016 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 7.33 g (0.02 mol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as 6FAP) was added together with 25 g of NMP, and reacted at 20°C for 1 hour. and then reacted at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 7 Synthesis of Polyimide Precursor (A-7)>
Under a dry nitrogen stream, 4.71 g (0.016 mol) of 4,4'-biphthalic anhydride (hereinafter referred to as BPDA) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 4.00 g (0.02 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 8 Synthesis of Polyimide Precursor (A-8)>
Under a stream of dry nitrogen, 7.11 g (0.016 mol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter referred to as 6FDA) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). let me 4.00 g (0.02 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 9 Synthesis of Polyimide Precursor (A-9)>
Under a stream of dry nitrogen, 8.33 g (0.016 mol) of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride (hereinafter referred to as BSAA) was added to N-methyl-2-pyrrolidone ( NMP) was dissolved in 100 g. 4.00 g (0.02 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Then, 0.78 g (0.008 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 10 Synthesis of polyimide (A-10)>
4.00 g (0.02 mol) of DAE was dissolved in 180 g of NMP under a stream of dry nitrogen. 4.96 g (0.016 mol) of ODPA was added together with 20 g of NMP, reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After stirring, the reaction solution was cooled to 60° C., 0.78 g (0.008 mol) of maleic anhydride was added together with 20 g of NMP, and reacted at 60° C. for 1 hour. The reaction solution was poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a ventilation dryer at 50° C. for three days to obtain polyimide (A-10) powder.

<Synthesis Example 11 Synthesis of polyimide (A-11)>
Under a stream of dry nitrogen, 7.33 g (0.02 mol) of 6FAP was dissolved in 180 g of NMP. 4.96 g (0.016 mol) of ODPA was added together with 20 g of NMP, reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After stirring, the reaction solution was cooled to 60° C., 0.78 g (0.008 mol) of maleic anhydride was added together with 20 g of NMP, and reacted at 60° C. for 1 hour. The reaction solution was poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a ventilation dryer at 50° C. for three days to obtain polyimide (A-11) powder.

<Synthesis Example 12 Synthesis of polyhydroxyamide (A-12)>
Under a dry nitrogen stream, 100 g of N-methylpyrrolidone was charged, 6FAP (7.33 g, 0.02 mol) was added, and after stirring and dissolving at room temperature, the temperature of the reaction solution was maintained at -10 to 0 ° C., and 4 ,4′-Diphenyletherdicarboxylic acid dichloride (4.72 g, 0.016 mol) was added and stirring continued at room temperature for 3 hours. 0.78 g (0.008 mol) of maleic anhydride was then added along with 20 g of NMP and allowed to react for 1 hour at room temperature. The reaction solution was poured into 1 liter of water, and the precipitate was collected, washed with pure water three times, and dried in a ventilation dryer at 50°C for 3 days to obtain polyhydroxyamide (A-12) powder. .

<Synthesis Example 13 Synthesis of Polyimide Precursor (A-13)>
Under a dry nitrogen stream, 4.34 g (0.014 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 4.00 g (0.02 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Then, 1.18 g (0.012 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 14 Synthesis of polyimide precursor (A-14)>
Under a dry nitrogen stream, 5.58 g (0.018 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 4.00 g (0.02 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Then, 0.39 g (0.004 mol) of maleic anhydride was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the solid polymer precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 15 Synthesis of Polyimide Precursor (B-1)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 1.73 g (0.016 mol) of PDA was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 16 Synthesis of polyimide precursor (B-2)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 3.20 g (0.016 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 17 Synthesis of polyimide precursor (B-3)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 5.12 g (0.016 mol) of TFMB was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 18 Synthesis of polyimide precursor (B-4)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 5.35 g (0.016 mol) of BIS-A-AF was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 19 Synthesis of polyimide precursor (B-5)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 4.13 g (0.016 mol) of BAP was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 20 Synthesis of polyimide precursor (B-6)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 5.86 g (0.016 mol) of 6FAP was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 21 Synthesis of polyimide precursor (B-7)>
Under a dry nitrogen stream, 5.88 g (0.02 mol) of BPDA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 3.20 g (0.016 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 22 Synthesis of polyimide precursor (B-8)>
Under a stream of dry nitrogen, 8.88 g (0.02 mol) of 6FDA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 3.20 g (0.016 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 23 Synthesis of polyimide precursor (B-9)>
Under a dry nitrogen stream, 10.41 g (0.02 mol) of BSAA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 3.20 g (0.016 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.95 g (0.008 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 24 Synthesis of polyimide (B-10)>
Under a stream of dry nitrogen, 3.20 g (0.016 mol) of DAE was dissolved in 180 g of NMP. 6.20 g (0.02 mol) of ODPA was added together with 20 g of NMP, reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After stirring, the reaction solution was cooled to 60° C., 0.95 g (0.008 mol) of 4-aminostyrene was added together with 20 g of NMP, and reacted at 60° C. for 1 hour. The reaction solution was poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in an air drier at 50° C. for three days to obtain polyimide (B-10) powder.

<Synthesis Example 25 Synthesis of polyimide (B-11)>
5.86 g (0.016 mol) of 6FAP was dissolved in 180 g of NMP under a stream of dry nitrogen. 6.20 g (0.02 mol) of ODPA was added together with 20 g of NMP, reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After stirring, the reaction solution was cooled to 60° C., 0.95 g (0.008 mol) of 4-aminostyrene was added together with 20 g of NMP, and reacted at 60° C. for 1 hour. The reaction solution was poured into 1 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in an air drier at 50° C. for three days to obtain polyimide (B-11) powder.

<Synthesis Example 26 Synthesis of polyhydroxyamide (B-12)>
Under a stream of dry nitrogen, 100 g of N-methylpyrrolidone was charged, 6FAP (5.86 g, 0.016 mol) was added, and dissolved with stirring at room temperature. ,4′-Diphenyletherdicarboxylic acid dichloride (5.90 g, 0.02 mol) was added and stirring continued at room temperature for 3 hours. Then, 0.96 g (0.008 mol) of 4-aminostyrene was added together with 20 g of NMP and reacted for 1 hour at room temperature. The reaction solution was poured into 1 liter of water, and the precipitate was collected, washed with pure water three times, and dried in a ventilation dryer at 50°C for 3 days to obtain polyhydroxyamide (B-12) powder. .

<Synthesis Example 27 Synthesis of polyimide precursor (B-13)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 2.80 g (0.014 mol) of DAE was added together with 25 g of NMP, and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 1.43 g (0.012 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

<Synthesis Example 28 Synthesis of polyimide precursor (B-14)>
Under a dry nitrogen stream, 6.20 g (0.02 mol) of ODPA was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). 3.60 g (0.018 mol) of DAE was added thereto together with 25 g of NMP and reacted at 20° C. for 1 hour and then at 50° C. for 2 hours. Next, 0.48 g (0.004 mol) of 4-aminostyrene was added and reacted at 50° C. for 2 hours. Thereafter, a solution of 7.15 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 10 g of NMP was added dropwise. After dropping, the mixture was stirred at 50°C for 3 hours. After completion of the reaction, the solution was poured into 1 L of water, and the polymer solid precipitate was collected by filtration and washed with water three times. ) (a polyamic acid ester) was obtained.

[Examples 1 to 12, 23, 24]
As shown in Table 1, a varnish was prepared by adding 20 g of NMP as a solvent to 5 g of component (A) and 5 g of component (B).

[Example 13]
A varnish was prepared by adding 20 g of NMP as a solvent to 2.5 g of A-2 and 7.5 g of B-2.

[Example 14]
A varnish was prepared by adding 20 g of NMP as a solvent to 7.5 g of A-2 and 2.5 g of B-2.

[Example 15]
A varnish was prepared by adding 20 g of NMP as a solvent to 2.5 g of A-12 and 7.5 g of B-12.

[Example 16]
A varnish was prepared by adding 20 g of NMP as a solvent to 7.5 g of A-12 and 2.5 g of B-12.

[Examples 17 and 18]
As shown in Table 1, to 5 g of component (A) and 5 g of component (B), 2.0 g of the following (C) photoacid generator, 3.0 g of (D) thermal cross-linking agent, and 20 g of γ-butyrolactone as a solvent were added. A varnish was produced by

[Examples 19 and 20]
As shown in Table 1, for 5 g of component (A) and 5 g of component (B), 1.5 g of the following (E) photopolymerization initiator, 4.5 g of (F) photopolymerizable compound, and 20 g of γ-butyrolactone as a solvent. In addition, a varnish was produced.

[Comparative Examples 1 and 3]
As shown in Table 1, a varnish was prepared by adding 20 g of NMP as a solvent to 10 g of component (A).

[Comparative Examples 2 and 4]
As shown in Table 1, a varnish was prepared by adding 20 g of NMP as a solvent to 10 g of component (B).

[Example 21]
A varnish was prepared by adding 20 g of NMP as a solvent to 1.5 g of A-2 and 8.5 g of B-2.

[Example 22]
A varnish was prepared by adding 20 g of NMP as a solvent to 8.5 g of A-2 and 1.5 g of B-2.

Table 1 shows the material amount ratio, molecular weight, breaking elongation, and crack evaluation results of the resin compositions obtained in Examples and Comparative Examples.

[Example 25]
A varnish was prepared by adding 1 g of G-1 and 20 g of NMP as a solvent to 5 g of A-2 and 5 g of B-2.

[Example 26]
A varnish was prepared by adding 1 g of G-2 and 20 g of NMP as a solvent to 5 g of A-2 and 5 g of B-2.

[Example 27]
A varnish was prepared by adding 1 g of G-2 and 20 g of NMP as a solvent to 5 g of A-11 and 5 g of B-11.

[Example 28]
A varnish was prepared by adding 1 g of G-2 and 20 g of NMP as a solvent to 5 g of A-12 and 5 g of B-12.

[Example 29]
A varnish was prepared by adding 0.5 g of G-2 and 20 g of NMP as a solvent to 5 g of A-11 and 5 g of B-11.

[Example 30]
A varnish was prepared by adding 10 g of G-2 and 20 g of NMP as a solvent to 5 g of A-11 and 5 g of B-11.

[Example 31]
A varnish was prepared by adding 0.5 g of G-3 and 20 g of NMP as a solvent to 5 g of A-11 and 5 g of B-11.

[Example 32]
A varnish was prepared by adding 0.5 g of G-4 and 20 g of NMP as a solvent to 5 g of A-11 and 5 g of B-11.

[Comparative Example 5]
A varnish was prepared by adding 0.3 g of G-3 and 20 g of NMP as a solvent to 10 g of A-11.

[Comparative Example 6]
A varnish was prepared by adding 1 g of G-3 and 20 g of NMP as a solvent to 10 g of A-11.

[Comparative Example 7]
A varnish was prepared by adding 1 g of G-3 and 20 g of NMP as a solvent to 10 g of the above and B-11.

[Comparative Example 8]
A varnish was prepared by adding 1 g of G-4 and 20 g of NMP as a solvent to 10 g of A-11.

Table 2 shows the breaking elongation and crack evaluation results of the resin compositions obtained in each example and comparative example.

The resin composition of the present invention can be used for surface protective films such as semiconductor elements, interlayer insulating films, insulating layers of display devices such as organic light-emitting elements, flattening films of thin film transistor (hereinafter referred to as TFT) substrates, and wiring protective insulating films of circuit boards. , on-chip microlenses of solid-state imaging devices, flattening films for various displays and solid-state imaging devices, and solder resists for circuit boards.

Claims

(A) A resin composition containing a resin represented by formula (1) and (B) a resin represented by formula (2).

(In formula (1), each X independently represents a repeating structural unit of polyamide, polyimide, polybenzoxazole or a precursor thereof, and R 1 is a monovalent represented by formula (3) or formula (4). R a represents a group selected from the group consisting of R 1 , a hydrogen atom, and a monovalent organic group having 1 to 20 carbon atoms, and n 1 is an integer of 2 to 200.)

(In formula (2), each Y independently represents a repeating structural unit of polyamide, polyimide, polybenzoxazole, or a precursor thereof, and R2 is a monovalent group represented by formula (5). R b represents a group selected from the group consisting of R 2 , a hydrogen atom, and a monovalent organic group having 1 to 20 carbon atoms, and n 2 is an integer of 2 to 200.)

(In formula (3), * represents a bond.)

(In formula (4), R 3 is a hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms. * represents a bond.)

(In formula (5), * represents a bond.)
The terminal group R of the component (A) when the total integral value of the signals derived from the hydrogen atoms of the amide bonds appearing at 9 to 11 ppm in the 1 H-NMR spectrum of the component (A) and the component (B) is taken as 100. The total integrated value of the signal derived from the hydrogen atom of 1 is defined as r 1 and the total integrated value of the signal derived from the hydrogen atom of the terminal group R 2 of component (B) is r 2 , and M = 3r 1 /2r 2 2. The resin composition according to claim 1, wherein M is 0.25 or more and 4 or less.
3. The resin composition according to claim 1, wherein the resin composition has a weight average molecular weight of 5,000 or more and 35,000 or less.
The repeating structural unit of polyimide is a repeating structural unit represented by formula (6),
The repeating structural unit of the polyamide, polyimide precursor or polybenzoxazole precursor is a repeating structural unit represented by formula (7), and the repeating structural unit of polybenzoxazole is a repeat represented by formula (8) The resin composition according to any one of claims 1 to 3, which is a structural unit.

(In formula (6), R 4 represents a tetravalent organic group having 4 to 40 carbon atoms, and R 5 represents a divalent organic group having 4 to 40 carbon atoms.)

(In formula (7), R 6 represents a divalent to octavalent organic group having 4 to 40 carbon atoms. R 7 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. R 8 represents a hydrogen atom. or represents a monovalent organic group having 1 to 20 carbon atoms, q and r are within the ranges of 0 ≤ q ≤ 4 and 0 ≤ r ≤ 4, and represent integers satisfying 0 ≤ q + r ≤ 6. s represents an integer from 0 to 2.)

(In formula (8), R 9 represents a divalent organic group having 4 to 40 carbon atoms, and R 10 represents a divalent organic group having 4 to 40 carbon atoms.)
R 4 in formula (6) and R 6 in formula (7) have a structure represented by formula (9),
5. The resin composition according to claim 4, wherein R5 in formula (6) and R7 in formula (7) are structures represented by formula (10).

(In formula (9), R 11 represents a single bond, —O—, —C(CF 3 ) 2 —, or the structure represented by formula (11). * represents a bond.)

(In formula (10), R 12 is represented by a single bond, —O—, —C(CH 3 ) 2 — or —C(CF 3 ) 2 —, and each R 13 is independently a hydrogen atom or a carbon number represents a monovalent organic group of 1 to 20. t and u each independently represent an integer of 0 to 4, satisfying t+u=4.* represents a bond.)

(In formula (11), R 14 represents a structure represented by a single bond, —O—, —C(CH 3 ) 2 — or —C(CF 3 ) 2 —. * represents a bond.)
R 9 in formula (8) is a structure represented by a single bond, a divalent hydrocarbon group having 1 to 6 carbon atoms, or a fluoroalkylene group having 1 to 6 carbon atoms, and R 10 is represented by formula (12 ). The resin composition according to claim 4 or 5, which has a structure represented by:

(In formula (12), R 15 represents a structure represented by a single bond, —O—, —C(CH 3 ) 2 — or —C(CF 3 ) 2 —. * represents a chemical bond.)
7. The resin composition according to any one of claims 1 to 6, further comprising a photoacid generator.
7. The resin composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator and a photopolymerizable compound.
9. The resin composition according to any one of claims 1 to 8, further comprising (G) a compound represented by formula (13).

(In formula (13), L 1 represents a structure represented by an alkylene group having 1 to 8 carbon atoms.)
A cured product obtained by curing the resin composition according to any one of claims 1 to 9.
A cured product containing a resin having a structure represented by formula (14) or (15).

(* represents a chemical bond.)
12. The cured product according to claim 11, containing a resin having a trifluoromethyl group.
A step of applying the resin composition according to any one of claims 7 to 9, a step of forming a pattern through an ultraviolet irradiation step and a development step, and a step of heating to form a relief pattern layer of a cured product. , a method for producing a cured product.
A semiconductor device comprising the cured product according to any one of claims 10 to 12.
An electronic component comprising the cured product according to any one of claims 10 to 12.
A display device comprising the cured product according to any one of claims 10 to 12.