Resin composition, resin sheet, cured film, method for manufacturing a cured film, semiconductor device, organic EL display device and display device

Abstract

A resin composition is provided that can impart resistance to a stripper for removing photoresist used during wiring formation and resistance to a constant temperature and humidity test (HAST), and also has excellent pattern shape of the cured film after heat treatment when it has photosensitivity. A resin composition comprising (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and copolymers thereof, (B) phenolic resin, and (C) a thermal crosslinking agent, wherein the (B) phenolic resin has structural units represented by a specific general formula (4), and the structural units represented by the general formula (4) have structural units of a specific general formula (5) and a specific general formula (6), and when the total number of structural units represented by the general formula (4) in the (B) phenolic resin is set to 100, the ratio of the number of structural units represented by the general formula (5) and the general formula (6) is general formula (5):general formula (6) = 60:40 to 90:10.

Description

Technology Field

[0001] The present invention relates to a resin composition used for a surface protective film or interlayer insulating film of a semiconductor device, an insulating layer of a display device such as an organic light-emitting diode, or a planarization film of a substrate of a thin-film transistor (hereinafter referred to as TFT). Background Technology

[0002] Conventionally, polyimide-based resins and polybenzoxazole-based resins, which have excellent heat resistance, electrical insulation, and mechanical properties, are widely used as surface protection films or interlayer insulating films for semiconductor devices, insulating layers for display devices such as organic light-emitting diodes, and planarization films for substrates of thin-film transistors (hereinafter referred to as TFTs).

[0003] Recently, in addition to the above characteristics, for polyimide-based resins and polybenzoxazole-based resins, high sensitivity is required for g-lines (436 nm), h-lines (405 nm), i-lines (365 nm), etc., used as exposure light sources in order to improve productivity.

[0004] Up until now, as a method for increasing sensitivity, examples include containing 101 parts by mass or more of novolak resin and / or polyhydroxystyrene resin with respect to 100 parts by mass of a polyimide precursor or a polybenzoxazole precursor (see Patent Document 1), and containing a phenol resin of a specific structure with respect to a polyimide precursor or a polybenzoxazole precursor (see Patent Documents 2 and 3).

[0005] In addition, to satisfy the heat resistance required in semiconductor manufacturing processes along with high sensitivity, a polybenzoxazole, a polybenzoxazole precursor, a polyimide, and a polyimide precursor containing a phenol resin of a specific structure has been proposed (see Patent Document 4). Prior art literature

[0006] Japanese Patent Publication No. 2005-352004, Japanese Patent Publication No. 2018-22171, Japanese Patent Publication No. 2018-55124, International Publication No. 2014 / 069091 The problem to be solved

[0007] However, in the composition described in the above literature, while sensitivity to exposure wavelength is improved, there were issues regarding pattern shape after curing at low temperature, resistance to strippers used to remove photoresist used during wiring formation, and resistance to constant temperature and humidity tests (HAST). means of solving the problem

[0008] To solve the above problem, the present invention has the following configuration.

[0009] [1] A resin composition comprising (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, (B) phenolic resin, and (C) a thermal crosslinking agent, wherein the (B) phenolic resin has a structural unit represented by general formula (4), the structural unit represented by general formula (4) has a structural unit of general formula (5) and general formula (6), and when the total number of structural units represented by general formula (4) in the (B) phenolic resin is set to 100, the ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 60:40 to 90:10.

[0010]

[0011] Among the general formula (4), R 25 , R 27 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 , R 27 If multiple of these exist, they may be identical or different. R 26It represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent integers from 0 to 3.

[0012]

[0013] Among the general formula (5), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3, and j3 represents an integer from 1 to 3.

[0014]

[0015] Among the general formula (6), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3.

[0016] [2] A resin sheet formed on a substrate using the above resin composition.

[0017] [3] The resin composition, or a cured film formed by curing the resin sheet.

[0018] [4] A method for manufacturing a cured film comprising the steps of: applying the resin composition to a substrate, or laminating the resin sheet to a substrate, and then drying to form a resin film; an exposure step for exposing the dried resin film; a development step for developing the exposed resin film; and a heat treatment step for heat treating the developed resin film.

[0019] [5] A semiconductor device having the above-mentioned hardened film.

[0020] [6] An organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarization layer or the insulating layer comprises the cured film.

[0021] [7] A display device having at least, metal wiring, the hardened film, and a plurality of light-emitting elements, wherein the light-emitting element has a pair of electrode terminals on one side, and the pair of electrode terminals are connected to a plurality of metal wirings extending into the hardened film, and the plurality of metal wirings maintain electrical insulation by the hardened film. Effects of the invention

[0022] The resin composition of the present invention has resistance to strippers used to remove photoresist used for wiring formation even during low-temperature heat treatment, resistance to constant temperature and humidity tests (HAST), and also has excellent pattern shape of the cured film after heat treatment. Brief explanation of the drawing

[0023] FIG. 1 is a front cross-sectional view showing one form of the display device of the present invention. FIG. 2 is a front cross-sectional view showing one form of the display device of the present invention in the form of a partition wall. Figure 3 is a front cross-sectional view of the opening pattern of the hardened film. FIG. 4 is a front cross-sectional view showing a separate embodiment of the display device of the present invention. Specific details for implementing the invention

[0024] The resin composition of the present invention comprises (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, (B) a phenolic resin, and (C) a thermal crosslinking agent, wherein the (B) phenolic resin has a structural unit represented by general formula (4), the structural unit represented by general formula (4) has a structural unit of general formula (5) and general formula (6), and when the total number of structural units represented by general formula (4) in the (B) phenolic resin is set to 100, the ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 60:40 to 90:10.

[0025]

[0026] Among the general formula (4), R 25 , R 27 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 , R 27 If multiple of these exist, they may be identical or different. R 26 It represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent integers from 0 to 3.

[0027]

[0028] Among the general formula (5), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3, and j3 represents an integer from 1 to 3.

[0029]

[0030] Among the general formula (6), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3.

[0031] One or more resins selected from the group consisting of (A) polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, which are contained in the resin composition of the present invention.

[0032] <(A) One or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof>

[0033] (A) One or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof may be referred to as component (A) below.

[0034] Polyimide is not particularly limited as long as it has an imide ring. Additionally, polyimide precursors are not particularly limited and may contain polyamic acid or polyamic acid esters, etc., as long as they have a structure that becomes a polyimide having an imide ring upon dehydration and ring closure. Polybenzoxazole is not particularly limited as long as it has an oxazole ring. Polybenzoxazole precursors are not particularly limited and may contain polyhydroxyamide, etc., as long as they have a structure that becomes a polybenzoxazole having a benzoxazole ring upon dehydration and ring closure.

[0035] Polyimide has a structural unit represented by general formula (1), polyimide precursor and polybenzoxazole precursor have a structural unit represented by the following general formula (2), and polybenzoxazole has a structural unit represented by general formula (15). Two or more of these may be contained, and a resin copolymerized with a structural unit represented by general formula (1), a structural unit represented by general formula (2), and a structural unit represented by general formula (15) may be contained.

[0036]

[0037] In general formula (1), V represents an organic group with 4 to 10 valence having 4 to 40 carbon atoms, and W represents an organic group with 2 to 8 valence having 4 to 40 carbon atoms. a and b each represent integers from 0 to 6. R 1 and R 2 represents a group selected from the group consisting of hydroxyl groups, carboxyl groups, sulfonic acid groups, and thiol groups, and multiple R 1 and R 2 They may be the same or different.

[0038]

[0039] In general formula (2), X and Y each independently represent an organic group having 4 to 40 carbon atoms and a 2 to 8 valence. R 3 and R 4Each represents independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. c and d each represent integers from 0 to 4, and e and f each represent integers from 0 to 2.

[0040]

[0041] In the general formula (15), T and U each independently represent an organic group with 4 to 40 carbon atoms and 2 to 8 valence.

[0042] (A) Specifically, polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers thereof may be preferably cited as components. These resins may be contained individually or in combination with multiple resins. These resins have high heat resistance and, since the amount of outgassing under temperature conditions of 160°C or higher after heat treatment is low, they are particularly suitable for use as planarization films, insulating layers, barriers, protective films, and interlayer insulating films used in organic light-emitting devices, display devices, and semiconductor devices.

[0043] In addition, although component (A) is not particularly limited, it is preferable that it be an alkali-soluble resin from the perspective of reducing environmental burden. Alkali solubility in the present invention is described. A solution in which a resin is dissolved in γ-butylolactone is applied onto a silicon wafer, and a pre-bake is performed at 120°C for 4 minutes to form a pre-bake film with a thickness of 10 μm ± 0.5 μm. Subsequently, the reduction in film thickness is determined when the pre-bake film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ± 1°C for 1 minute and then rinsed with pure water. A resin having a dissolution rate of 50 nm / min or more of the pre-bake film is defined as alkali-soluble.

[0044] (A) In order to make the component alkali solubility, it is preferable that general formula (1) has a+b>0. Also, it is preferable that general formula (2) has c+d+e+f>0. In the case of a polyimide precursor in general formula (2), it is preferable that X and Y in general formula (2) have aromatic groups. Furthermore, it is more preferable that X in general formula (2) has an aromatic group, e>0, has a carboxyl group or a carboxyester group at the ortho position of the aromatic amide group, and has a structure that forms an imide ring by dehydration and ring closure.

[0045] In addition, in the case of a polybenzoxazole precursor in the general formula (2), it is more preferable that X in the general formula (2) has an aromatic group, d>0, has a hydroxyl group at the ortho position of the aromatic amide group, and has a structure that forms a benzoxazole ring by dehydration and ring closure.

[0046] (A) In the component, the number of repetitions (n) of the structural unit represented by general formula (1) or (2) is preferably 5 to 100,000, and more preferably 10 to 100,000.

[0047] In addition, component (A) may have other structural units in addition to the structural unit represented by general formula (1) or (2). Examples of other structural units include cardo structures, siloxane structures, etc., but are not limited to these. In this case, it is preferable to have the structural unit represented by general formula (1), (2), or (15) as the main constituent unit. Here, the main constituent unit refers to having 50 mol% or more of the structural unit represented by general formula (1), (2), or (15) among the total number of structural units, and it is more preferable to have 70 mol% or more.

[0048] Residue of the acid of component (A)

[0049] Among the above general formula (1), V-(R 1 ) a, among the above general formula (2), (OH) c -X-(COOR 3 ) e , and, in the above general formula (15), T represents a residue of acid. V is a tetravalent to 10-valent organic group having 4 to 40 carbon atoms, and among them, an organic group having 4 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferred. X and T are 2 to 8-valent organic groups having 4 to 40 carbon atoms, and among them, an organic group having 4 to 40 carbon atoms containing an aromatic ring or an aliphatic group is preferred.

[0050] As acidic components constituting the residue of the acid, examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, souveric acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecane diacid, nonadecane diacid, eicosan diacid, hen-eicosan diacid, docosan diacid, tricosan diacid, tetracosan diacid, pentacosan diacid, hexacosan diacid, heptadecane diacid, octadecane diacid, Nonacoustic acid, triacontanic acid, etc., examples of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., examples of tetracarboxylic acids such as pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic 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 aromatics of the structure shown below Examples include tetracarboxylic acid, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, etc., but are not limited to these.You may use two or more of these.

[0051]

[0052] During the meal, R 17 represents an oxygen atom, C(CF3)2, or C(CH3)2. R 18 and R 19 represents a hydrogen atom, or a hydroxyl group.

[0053] These acids can be used as they are, or as acid anhydrides, halides, or active esters.

[0054] Residue of the diamine of component (A)

[0055] W-(R in the above general formula (1) 2 ) b , (OH) in the above general formula (2) d -Y-(COOR 4 ) f , and, U in the above general formula (15) represents a residue of diamine. W, Y, and U are organic groups having 2 to 8 carbon atoms with 4 to 40 carbon atoms, and among them, organic groups having 4 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group are preferred.

[0056] Specific examples of diamines constituting the residue of a diamine 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-aminophenoxy)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, Examples include 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-aminophenyl)fluorene, or compounds in which at least some of the hydrogen atoms of the aromatic rings of these are substituted with alkyl groups or halogen atoms, aliphatic diamines, and diamines having the structure shown below. Two or more of these may be used.

[0057]

[0058] During the meal, R 20 represents an oxygen atom, C(CF3)2, or C(CH3)2. R 21 ~R 24 Each represents a hydrogen atom or a hydroxyl group independently.

[0059] These diamines can be used as diamines, or as diisocyanate compounds obtained by reacting diamines with phosgene, or as trimethylsilylated diamines.

[0060] <Group selected from alkylene groups and alkylene ether groups>

[0061] In addition, component (A) preferably contains a group selected from alkylene groups and alkylene ether groups. These groups may include aliphatic rings. As for the group selected from alkylene groups and alkylene ether groups, the group represented by general formula (3) is particularly preferred.

[0062]

[0063] Among the general formula (3), R 5 ~R 8 Each independently represents an alkylene group having 1 to 6 carbon atoms. R 9 ~R 16 Each represents independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms. However, the structures shown in parentheses are distinct. g, h, and i each represent independently integers from 0 to 35, and g+h+i>0.

[0064] Examples of groups represented by the general formula (3) include ethylene oxide, propylene oxide, butylene oxide, etc., and any of straight chain, branched, and cyclic forms are acceptable.

[0065] (A) Since the component has a group selected from alkylene groups and alkylene ether groups, imide ring-closing and benzoxazole ring-closing reactions are promoted even during low-temperature heat treatment, thereby improving chemical resistance. In addition, since interactions such as coordination bonding are obtained between the alkylene groups and alkylene ether groups and the metal, high adhesion to the substrate metal can be obtained. Furthermore, since polarity can be lowered by introducing alkylene groups and alkylene ether groups, resistance to the heat-and-numerical test (HAST) can be improved.

[0066] (A) It is preferable that the component contains a group selected from the alkylene group and the alkylene ether group in W in the general formula (1) or Y in the general formula (2). By doing so, high chemical resistance, high adhesion to the substrate metal, and resistance to the constant temperature and humidity test (HAST) can be obtained by promoting ring closure in the low-temperature heat treatment of the cured film of the resin composition.

[0067] Specific examples of diamines containing a group selected from alkylene groups and alkylene ether groups include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane. Examples include 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700 (product names, manufactured by HUNTSMAN Co., Ltd.).

[0068] In addition, among these diamines, bonds such as -S-, -SO-, -SO2-, -NH-, -NCH3-, -N(CH2CH3)-, -N(CH2CH2CH3)-, -N(CH(CH3)2)-, -COO-, -CONH-, -OCONH-, -NHCONH-, etc. may be included.

[0069] Diamine residues containing a group selected from alkylene groups and alkylene ether groups are preferably included in an amount of 5 mol% or more of the total diamine residues, and more preferably in an amount of 10 mol% or more. In addition, it is preferable to include 40 mol% or less of the total diamine residues, and more preferable to include 30 mol% or less. By including them within the above ranges, it is possible to improve developability in an alkaline developer, as well as obtain high chemical resistance, high adhesion to the substrate metal, and resistance to the heat-and-stress test (HAST) by promoting ring closure during low-temperature heat treatment.

[0070] In addition, diamine residues having an aliphatic polysiloxane structure may be copolymerized within a range that does not reduce heat resistance. Adhesion to the substrate can be improved by copolymerizing diamine residues having an aliphatic polysiloxane structure. Specifically, examples include a copolymer of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., in an amount of 1 to 15 mol% of the total diamine residues as the diamine component. Copolymerizing within this range is preferable in that it improves adhesion to a substrate such as a silicon wafer and does not reduce solubility in an alkaline solution.

[0071] In addition, by sealing the end of component (A) with a monoamine having an acidic group, an acid anhydride, an acid chloride, or a monocarboxylic acid, a resin having an acidic group at the end of the main chain can be obtained. Known monoamines having acidic groups, acid anhydrides, acid chlorides, and monocarboxylic acids may be used, or multiple may be used.

[0072] The content of the terminal sealant, such as the monoamine, acid anhydride, acid chloride, and monocarboxylic acid, is preferably 2 to 25 mol% with respect to the total sum of 100 mol% of the acid component and amine component constituting component (A).

[0073] (A) It is preferable that the component has a weight average molecular weight of 10,000 or more and 100,000 or less. If the weight average molecular weight is 10,000 or more, the mechanical properties of the cured film after curing can be improved. More preferably, the weight average molecular weight is 20,000 or more. Meanwhile, it is preferable that the weight average molecular weight is 100,000 or less so that the developability with various developers can be improved, and also that the weight average molecular weight is 50,000 or less so that the developability with alkaline solutions can be improved.

[0074] The weight-average molecular weight (Mw) can be determined using GPC (gel permeation chromatography). For example, it can be measured using N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) as the developing solvent and obtained by polystyrene conversion.

[0075] (A) The content of component A is preferably 3 to 55 mass% of the total content of 100 mass% including the solvent, and more preferably 5 to 40 mass%. By maintaining the above range, the viscosity can be made suitable for spin coating or slit coating.

[0076] <Production of Component (A)>

[0077] (A) The component can be produced by known methods.

[0078] In the case of a polyimide precursor, such as a polyamic acid or a polyamic acid ester, the first method involves reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature. The second method involves obtaining a diester by reacting the tetracarboxylic acid dianhydride with an alcohol. Then, the diester is reacted in the presence of an amine and a condensation agent. The third method involves obtaining a diester by reacting the tetracarboxylic acid dianhydride with an alcohol. Then, the remaining dicarboxylic acid is acidified and reacted with an amine. The product can be synthesized in this manner.

[0079] In the case of polybenzoxazole precursors, such as polyhydroxyamides, they can be obtained by a manufacturing method in which a bisaminophenol compound is condensed with a dicarboxylic acid. Specifically, there are methods such as reacting an acid with a dehydration condensation agent like dicyclohexylcarbodiimide (DCC) and adding a bisaminophenol compound thereto, or adding a solution of a dicarboxylic acid dichloride dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0080] In the case of polyimide, for example, it can be obtained by dehydrating and ring-closing a polyimide precursor obtained by the above-described method through heating or chemical treatment such as acid or base.

[0081] The resin composition of the present invention may include other alkali-soluble resins in addition to component (A). Specifically, other alkali-soluble resins may include siloxane polymers, cyclic olefin polymers, and cardo resins. These resins may be used individually or in combination. In that case, when the total of component (A) and other alkali-soluble resins is 100 parts by mass, it is preferable that the content ratio of other alkali-soluble resins be 1 to 50 parts by mass.

[0082] <(B) Phenolic Resin>

[0083] <Phenol resin containing a structural unit represented by general formula (4)>

[0084] The resin composition of the present invention contains (B) a phenolic resin (hereinafter referred to as component (B)), and the (B) phenolic resin has a structural unit represented by the general formula (4).

[0085]

[0086] Among the general formula (4), R 25 , R 27 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R25 , R 27 If multiple of these exist, they may be identical or different. R 26 It represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent integers from 0 to 3.

[0087] As shown in the above general formula (4), by using a phenol resin obtained from a phenol compound and an aromatic aldehyde compound and / or an aromatic ketone compound, excellent heat resistance can be provided, as well as resistance to a stripper used to remove photoresist used when forming wiring. In addition, when it has photosensitivity, the contrast difference between the exposed and unexposed parts during development is large, and the glass transition temperature of the resin film is appropriately raised, so the pattern shape of the resin film after development and the cured film after heat treatment is excellently tapered.

[0088] In addition, the structural unit represented by the above general formula (4) has the structural units of the general formula (5) and the general formula (6), and when the total number of structural units represented by the general formula (4) in (B) the phenol resin is set to 100, the ratio of the number of structural units represented by the general formula (5) to the number of structural units represented by the general formula (6) is general formula (5):general formula (6) = 60:40 to 90:10.

[0089]

[0090] Among the general formula (5), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3, and j3 represents an integer from 1 to 3.

[0091]

[0092] Among the general formula (6), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3.

[0093] By setting it to the above range, appropriate developability is imparted, and even with low-temperature heat treatment, resistance to strippers used to remove photoresist used for wiring formation and photosensitivity are provided, resulting in excellent pattern shape of the resin film after development and the cured film after heat treatment.

[0094] <Phenol Compounds>

[0095] Examples of phenol compounds include phenol as an example of alkylphenols; metacresol, paracresol, orthocresol, xylenol, ethylphenol, butylphenol, octylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, etc. Examples of polyvalent phenols include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, etc. Examples of other phenols include halogenated phenols, phenylphenol, aminophenol, etc. Among these, a phenol compound represented by the following formula (7) is more preferred. These phenol compounds may be used alone, or a combination of multiple phenol compounds may be used.

[0096]

[0097] Aromatic aldehyde compounds

[0098] Examples of aromatic aldehyde compounds used in the structural unit represented by the general formula (5) include 4-methoxybenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsalicylaldehyde, 4-methylsalicylaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, etc. Among these, the aromatic aldehyde compound represented by the following formula (8) is more preferred. These aromatic aldehyde compounds may be used alone, or a combination of multiple aromatic aldehyde compounds may be used.

[0099]

[0100] As for the aromatic aldehyde compounds used in the structural unit represented by the general formula (6), examples include benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3,4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, Examples include 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, 4-isobutylbenzaldehyde, etc. Among these, an aromatic aldehyde compound represented by the following formula (9) is more preferred. These aromatic aldehyde compounds may be used alone, or a combination of multiple aromatic aldehyde compounds may be used.

[0101]

[0102] Aromatic ketone compounds

[0103] As aromatic ketone compounds used in the structural unit represented by general formula (5), for example, p-hydroxyacetophenone, m-hydroxyacetophenone, 3',5'-dihydroxyacetophenone, p-hydroxypropiophenone, m-hydroxypropiophenone, p-hydroxyvalerophenone, 1'-hydroxy-2'-acetonaftone, 2'-hydroxy-1'-acetonaftone, 2'-hydroxy-5'-methylacetophenone, 4'-hydroxy-2'-methylacetophenone, 4'-hydroxy-3'-methylacetophenone, 2',4'-dihydroxy-3'-methylacetophenone, 2'-hydroxy-4',5'-dimethylacetophenone, 4'-Benzoyloxy-2'-Hydroxy-3'-Methylacetophenone, 4'-Benzyloxy-2'-Methoxy-3'-Methylacetophenone, 2'-Hydroxy-4'-Methoxyacetophenone, 2'-Hydroxy-5'-Methoxyacetophenone, 2'-Hydroxy-6'-Methoxyacetophenone, 2-(Phenylsulfonyl)acetophenone, 2-Hydroxy-2-Methylpropiophenone, 2',4'-Dihydroxy-3'-Methylpropiophenone, 2-Hydroxy-4'-(2-Hydroxyethoxy)-2-Methylpropiophenone, 2'-Hydroxy-3-Phenylpropiophenone, 4'-Benzyloxy-2'-Hydroxy-3'-Methylpropiophenone, 2',4'-Dihydroxy-3'-Methylbutyrophenone, o-Hydroxybenzophenone, p-Hydroxybenzophenone, 2,4-Dihydroxybenzophenone, 2,2'-Dihydroxybenzophenone, 2,4-Dihydroxybenzophenone, 4,4'-Dihydroxybenzophenone, 2,3,4-Trihydroxybenzophenone, 2,4,4'-Trihydroxybenzophenone, 2,2',4,4'-Tetrahydroxybenzophenone, 4-Fluoro-4'-Hydroxybenzophenone, Benzyl-4-Hydroxyphenylketone, 2-Hydroxy-5-Methylbenzophenone, 2-Hydroxy-4-Methoxybenzophenone, Examples include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 5-hydroxy-1-tetraron, etc. Among these, an aromatic ketone compound represented by the following formula (10) is more preferred. These aromatic ketone compounds may be used alone, or a combination of multiple aromatic ketone compounds may be used.

[0104]

[0105] As aromatic ketone compounds used in the structural unit represented by general formula (6), examples include acetophenone, propiophenone, butyrophenone, isobutyrophenone, valerophenone, hexanophenone, 2,2-dimethylpropiophenone, 2-phenylbutyrophenone, phenylvinylketone, cyclohexylphenylketone, p-methylacetophenone, m-methylacetophenone, o-methylacetophenone, p-ethylacetophenone, p-propylacetophenone, p-isobutylacetophenone, p-butylacetophenone, pt-butylacetophenone, 2',4'-dimethylacetophenone, 3',4'-dimethylacetophenone, 2',4',6'-trimethylacetophenone, p-methylpropiophenone, m-methylpropiophenone, o-methylpropiophenone, p-ethylpropiophenone, m-ethylpropiophenone, o-ethylpropiophenone, pt-butylpropiophenone, 1'-acetonaftone, 2'-acetonaftone, 6'-methyl-2'-acetonaftone, 4-acetylbiphenyl, t-butyl-4-phenoxyphenylketone, 1-(2-naphthyl)-3-phenyl-2-propen-1-one, 2-fluoroacetophenone, p-fluoroacetophenone, m-fluoroacetophenone, o-fluoroacetophenone, m-trifluoromethylacetophenone, 2-fluoropropiophenone, 3-fluoropropiophenone, p-fluoropropiophenone, m-fluoropropiophenone, o-fluoropropiophenone, p-methoxyacetophenone, m-methoxyacetophenone, o-methoxyacetophenone, 2-methoxyacetophenone, p-ethoxyacetophenone, p-phenoxyacetophenone, 2',2'-diethoxyacetophenone, 2',4'-dimethoxyacetophenone, 2',5'-dimethoxyacetophenone, 2',6'-dimethoxyacetophenone, 3',4'-dimethoxyacetophenone, 3',5'-dimethoxyacetophenone, 3',4'-(methylenedioxy)acetophenone, 3',4'-(methylenedioxy)propiophenone, 6'-methoxy-2'-acetonaftone, 6'-methoxy-2'-propiononaftone, 2',4'-dimethoxy-3'-methylacetophenone, 2,2-Dimethoxy-2-Phenylacetophenone, 5'-Fluoro-2'-Hydroxyacetophenone, 3',5'-Dimethoxy-4'-Hydroxyacetophenone, 2-Fluoro-p-Methoxyacetophenone, 2-Fluoro-m-Methoxyacetophenone,2-Fluoro-o-methoxyacetophenone, 2'-Fluoro-4'-methoxyacetophenone, 3'-Fluoro-4'-methoxyacetophenone, 2',4'-Dimethoxy-3'-methylpropiophenone, Benzophenone, Anthraquinone, p-Methylbenzophenone, m-Methylbenzophenone, o-Methylbenzophenone, p-Ethylbenzophenone, m-Ethylbenzophenone, o-Ethylbenzophenone, 2,5-Dimethylbenzophenone, 2,4-Dimethylbenzophenone, 3,4-Dimethylbenzophenone, p-Morfollinobenzophenone, p-Phenylbenzophenone, o-Fluorobenzophenone, p-Fluorobenzophenone, 2,4'-Difluorobenzophenone, p-Methoxybenzophenone, 4,4'-Dimethoxybenzophenone, Examples include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-(p-triylthio)benzophenone, 1-indanone, 2-methyl-1-indanone, 3-methyl-1-indanone, 4-methoxy-1-indanone, 5-methoxy-1-indanone, 6-methoxy-1-indanone, 4-hydroxy-1-indanone, α-tetraron, 1-benzosuberone, etc. Among these, an aromatic ketone compound represented by the following formula (11) is more preferred. These aromatic ketone compounds may be used alone, or a combination of multiple aromatic ketone compounds may be used.

[0106]

[0107] In the present invention, the aromatic aldehyde compound and the aromatic ketone compound may be used alone or in combination. Furthermore, regarding the ratio of the phenol compound and the aromatic aldehyde compound and / or aromatic ketone compound, it is preferable to set the [aromatic aldehyde compound and / or aromatic ketone compound] / [phenol compound] to a molar ratio of 0.5 to 2.0, as this results in a novolak-type phenol resin with a low amount of unreacted phenols and sufficiently high molecular weight, and a range of 0.7 to 1.8 is more preferable.

[0108] In the present invention, it is preferable to use an acid catalyst for the polycondensation reaction of component (B). Examples of acid catalysts used include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, etc., and organic acids such as oxalic acid, acetic acid, p-toluenesulfonic acid, etc.

[0109] (B) The component preferably has a weight average molecular weight of 500 or more and 10,000 or less, and more preferably has a weight average molecular weight of 500 or more and 5,000 or less. When the weight average molecular weight is within the above range, it has compatibility with component (A), heat resistance, suitable developability, and photosensitivity, so that the resin film after development and the cured film after heat treatment can have excellent pattern shapes and resistance to strippers used to remove photoresist when forming wiring.

[0110] The weight-average molecular weight (Mw) can be determined using GPC (gel permeation chromatography). For example, it can be measured using N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) as the developing solvent and obtained by polystyrene conversion.

[0111] <Preparation of Component (B)>

[0112] The above component (B) can be prepared by known methods, but is typically prepared using a polycondensation reaction. The polycondensation reaction is carried out by stirring for several hours under heating in the presence of the above acid catalyst. The reaction temperature is preferably 50°C to 140°C. In addition, a solvent may be added during the reaction to carry out the reaction in a solvent. As reaction solvents, for example, as alcohol-based solvents, methanol, ethanol, propanol, etc.; as polyol-based solvents, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.; as glycol ether-based solvents, 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol monophenyl ether, etc.; as cyclic ether-based solvents, 1,3-dioxane, Examples of solvents include 1,4-dioxane tetrahydrofuran, dioxane, etc., glycol ester solvents such as ethylene glycol acetate, diethylene glycol monomethyl ether acetate, etc., ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., aromatic hydrocarbons such as toluene, xylene, etc., and other solvents such as γ-butylolactone, pure water, etc., but are not limited to these. These solvents may be used as a single type or two or more types may be used in combination.

[0113] The amount of solvent added is preferably 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of the phenol compound.

[0114] After the reaction is complete, the acid catalyst is neutralized using a base such as pyridine, triethylamine, or sodium hydroxide, and if necessary, the neutralized salt is removed by extraction into the aqueous layer, after which the product is recovered through dehydration and monomer removal processes.

[0115] After the synthesis of the above phenol resin (B), a monomer removal process is typically performed. The monomer removal method may be selected from a solvent fractionation method, which removes the water layer by adding a solvent and water, or a method of volatilizing the monomer by heating under reduced pressure.

[0116] In addition, as a method for producing other (B) components, a method involving the following three processes may be used.

[0117] Process 1

[0118] A phenolic trinucleus compound is obtained by heating the above phenol compound and the above aromatic aldehyde compound or aromatic ketone compound in the presence of the above acid catalyst, using a solvent as needed, in the range of 60 to 140°C and polycondensing them.

[0119] Process 2

[0120] The phenolic trinucleated compound obtained in Process 1 is isolated from the reaction solution.

[0121] Process 3

[0122] The phenolic trinucleus compound isolated in Process 2 and the aromatic aldehyde compound and / or aromatic ketone compound are heated in the presence of the acid catalyst, using a solvent as needed, in the range of 60 to 140°C and polycondensed to obtain a phenolic resin.

[0123] It is desirable to use a phenolic trinucleus compound because, due to the narrow molecular weight distribution, it has resistance to strippers used to remove photoresist used for wiring formation even at low temperature heat treatment, and photosensitivity, so the pattern shape of the resin film after development and the cured film after heat treatment is excellent.

[0124] After the reaction is finished for processes 1 and 3, the acid catalyst is neutralized using a base such as pyridine, triethylamine, or sodium hydroxide, and if necessary, the neutralized salt is removed by extraction into the aqueous layer, and then recovered through dehydration, monomer removal, isolation, etc.

[0125] The input ratio [phenol compound / (aromatic aldehyde compound or aromatic ketone compound)] of the phenol compound and the aromatic aldehyde compound or aromatic ketone compound in process 1 is preferably in the range of 1 / 0.2 to 1 / 0.5 in molar ratio, and more preferably in the range of 1 / 0.25 to 1 / 0.45, due to the excellent removal of unreacted phenol compound, product yield, and purity of the reaction product.

[0126] As a method for isolating a phenolic trinucleate compound from a reaction solution in Process 2, for example, a method may be used in which the reaction solution is introduced into a poor solvent in which the reaction product is insoluble or sparingly soluble, the resulting precipitate is filtered and separated, the reaction product is dissolved in a solvent that is miscible with the poor solvent, and the resulting precipitate is introduced into the poor solvent again and filtered and separated. Examples of the poor solvents used at this time include water, monoalcohols such as methanol, ethanol, and propanol, aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane, and aromatic hydrocarbons such as toluene and xylene. Among these poor solvents, water and methanol are preferred because they allow for the efficient simultaneous removal of the acid catalyst. Meanwhile, as the above solvent, for example, as a polyol-based solvent, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.; as a glycol ether-based solvent, 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol monophenyl ether, etc.; as a cyclic ether-based solvent, 1,3-dioxane, 1,4-dioxane tetrahydrofuran, dioxane, etc. Examples of glycol ester solvents include ethylene glycol acetate, diethylene glycol monomethyl ether acetate, etc., ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and other solvents include γ-butylolactone, etc. Each may be used individually or in combination of two or more types. A phenolic trinucleated compound can be obtained by the isolation method of Process 2 above.

[0127] Regarding the ratio of the phenolic trinucleated compound and the aromatic aldehyde compound and / or aromatic ketone compound used in process 3, the molar ratio of [phenolic trinucleated compound] / [aromatic aldehyde compound and / or aromatic ketone compound] is preferably in the range of 1 / 0.5 to 1 / 1.2 and more preferably in the range of 1 / 0.6 to 1 / 0.9, as this can suppress excessive high molecular weight (gelation) and obtain a product of appropriate molecular weight.

[0128] As solvents used as necessary in the above processes 1 and 3, for example, as alcohol-based solvents such as methanol, ethanol, propanol, etc.; as polyol-based solvents such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.; as glycol ether-based solvents such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethylmethyl ether, ethylene glycol monophenyl ether, etc.; and as cyclic ether-based solvents Examples include 1,3-dioxane, 1,4-dioxanetetrahydrofuran, dioxane, etc.; glycol ester solvents such as ethylene glycol acetate, diethylene glycol monomethyl ether acetate, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; and other solvents such as γ-butylolactone, pure water, etc., but are not limited to these. These solvents may be used as a single type or in combination of two or more types.

[0129] The content of component (B) is preferably 5 parts by mass or more and 10 parts by mass or more per 100 parts by mass of component (A), from the perspective of excellent pattern shape of the cured film after heat treatment and resistance to strippers used to remove photoresist used when forming wiring. In addition, from the perspective of compatibility with component (A), 200 parts by mass or less and 150 parts by mass or less per 100 parts by mass of component (A) are preferable.

[0130] <(C) Thermal crosslinking agent>

[0131] The resin composition of the present invention contains (C) a thermal crosslinking agent. A thermal crosslinking agent refers to a resin or compound having at least two thermally reactive functional groups, which are thermal crosslinking groups, within its molecule.

[0132] Specific examples of thermal crosslinking groups include cyclic ether groups, alkoxymethyl groups, methylene groups, etc.

[0133] (C) It is preferable that the thermal crosslinking agent contains a thermal crosslinking agent having a biphenyl structure that may have a substituent and / or a thermal crosslinking agent having a structural unit represented by the general formula (14) described later.

[0134] <Thermal crosslinking agents having a biphenyl structure that may have substituents>

[0135] The resin composition of the present invention preferably contains (C) a thermal crosslinking agent having a biphenyl structure that may have a substituent as a thermal crosslinking agent.

[0136] By having a biphenyl structure that may have substituents, the chemical resistance of the cured film against strippers, etc. can be improved, and since low water absorption can be imparted, resistance to the constant temperature and humidity test (HAST), etc. can be improved. In addition, since fluidity can be imparted by appropriately lowering the glass transition temperature of the resin film or cured film, the control of the pattern shape of the resin film after development and the cured film after heat treatment is excellent.

[0137] (C) Among the thermal crosslinking agents, it is preferable that the thermal crosslinking agent having a biphenyl structure that may have a substituent contains the structure of general formula (12) or general formula (13).

[0138] As for biphenyl structures that may have substituents, structures represented by general formula (12) and general formula (13) are preferred because they improve chemical resistance and also improve resistance to constant temperature and humidity tests (HAST).

[0139]

[0140] Among the general formula (12), R 29 and R 30 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 29 , R 30 If multiple of these exist, they may be identical or different. R 31 , R 32 represents a thermal crosslinker. m1 and m2 each independently represent integers from 0 to 4, and m3 and m4 each independently represent integers from 1 to 3, satisfying 1 ≤ m1 + m3 ≤ 5 and 1 ≤ m2 + m4 ≤ 5.

[0141]

[0142] Among the general formula (13), R 33 , R 34 , R 35 and R 36 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 33 , R 34 , R 35 and R 36 If multiple of these exist, they may be identical or different. R 37 , R 38 , R 39 and R 40 represents a thermal crosslinker. R 41n represents a monovalent organic group having 1 to 10 carbon atoms. n1, n4, n5, and n8 are each independently integers from 1 to 3, n2, n3, n6, and n7 are each independently integers from 0 to 4, n9 represents a repeating unit and is an integer from 1 to 10, and n10 represents an integer of 0 or 1.

[0143] Specific examples of the structure represented by general formula (12) and general formula (13) include the following cyclic ether compounds, methylene compounds, or alkoxymethyl compounds in which a hydrogen atom of a methylene group is substituted with a methyl group or an alkyl group having 2 to 10 carbon atoms, but are not limited to these. A copolymer may also be used.

[0144]

[0145]

[0146] n9 represents the repetition unit and is an integer from 1 to 10.

[0147] In the present invention, other thermal crosslinking agents may include known cyclic ether compounds, alkoxymethyl compounds, and methylene compounds.

[0148] <Thermal crosslinking agent having a structural unit represented by the general formula (14)>

[0149] The resin composition of the present invention preferably contains a thermal crosslinking agent having a structural unit represented by the general formula (14).

[0150]

[0151] Among the general formula (14), R 42 is a divalent organic group having an alkylene group or an alkylene ether group having 1 to 15 carbon atoms, R 43 and R 44 Each represents a hydrogen atom or a methyl group independently.

[0152] A thermal crosslinking agent having a structural unit represented by the general formula (14) can improve chemical resistance to strippers of cured films and impart low water absorption, thereby improving resistance to constant temperature and humidity tests (HAST). In addition, since fluidity can be imparted by appropriately lowering the glass transition temperature of the resin film or cured film, the control of the pattern shape of the resin film after development and the cured film after heat treatment is excellent.

[0153] Examples of crosslinking groups included in a thermal crosslinking agent having a structural unit represented by the general formula (14) include, but are not limited to, acrylic groups, methylene groups, alkoxymethyl groups, and cyclic ether groups. Among these, cyclic ether groups are preferred because they can react with the hydroxyl groups of component (A) to improve the heat resistance of the cured film and can react without dehydration.

[0154] Compounds containing structural units represented by the general formula (14) may be specifically exemplified as follows, but are not limited to the following structures.

[0155]

[0156] o during food 2 is an integer from 1 to 5, o 1 It is 1 to 20, and from the perspective of chemical resistance, low absorption, and control of pattern shape, o 2 is 1~2, o 1 It is desirable that it be 3 to 7.

[0157] (C) As a thermal crosslinking agent, a thermal crosslinking agent having a biphenyl structure that may have a substituent and / or a thermal crosslinking agent having a structural unit represented by the general formula (14), and other thermal crosslinking agents may be included in combination of two or more types.

[0158] (C) When the total amount of the thermal crosslinking agent is 100 mass%, it is preferable that the content ratio of the thermal crosslinking agent having a biphenyl structure that may have substituents and the thermal crosslinking agent having a structural unit represented by the general formula (14) be 15 mass% or more and 80 mass% or less. This can improve the chemical resistance of the cured film to strippers, etc., and also improve resistance to the constant temperature and humidity test (HAST), etc. because it can impart low water absorption. In addition, since the glass transition temperature of the resin film or the cured film is appropriately lowered, the control of the pattern shape of the cured film is excellent when it has photosensitive properties.

[0159] The resin composition of the present invention preferably contains a thermal crosslinking agent having a biphenyl structure that may have the substituent (C), and the content of the thermal crosslinking agent having a biphenyl structure that may have the substituent is preferably 30 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the phenol resin (B).

[0160] The content of (C) a thermal crosslinking agent having a biphenyl structure that may have substituents is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, with respect to resistance to strippers used to remove photoresist used during wiring formation and resistance to constant temperature and humidity tests (HAST), etc., with respect to 100 parts by mass of (B) phenol resin. In addition, with respect to resistance to strippers used to remove photoresist used during wiring formation and resistance to constant temperature and humidity tests (HAST), etc., while maintaining the pattern shape, it is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less, with respect to 100 parts by mass or less, with respect to 100 parts by mass or less.

[0161] <(D) Photosensitive Compound>

[0162] The resin composition of the present invention preferably contains (D) a photosensitive compound (hereinafter referred to as component (D)).

[0163] Photosensitivity can be imparted to the resin composition by including component (D). Component (D) is a compound whose chemical structure changes in response to ultraviolet light, and examples include photogenerators, photobase generators, and photopolymerization initiators. When a photogenerator is used as component (D), acid is generated in the irradiated portion of the photosensitive resin composition, and since the solubility of the irradiated portion in the alkaline developer increases, a positive type pattern in which the irradiated portion dissolves can be obtained.

[0164] (D) When a photobase generating agent is used as a component, a base is generated in the light-irradiated portion of the resin composition, and since the solubility of the light-irradiated portion in the alkaline developer is reduced, a negative type pattern in which the light-irradiated portion becomes insoluble can be obtained.

[0165] (D) When a photopolymerization initiator is used as a component, radicals are generated in the light-irradiated portion of the resin composition, radical polymerization proceeds, and a negative-type pattern can be formed by becoming insoluble in the alkaline developer. In addition, UV curing during exposure is promoted, which can improve sensitivity.

[0166] Among the above-mentioned (D) components, a photogenerator is preferred in that a high-resolution pattern is obtained with high sensitivity. Examples of photogenerators include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodinium salts, etc. Additionally, a sensitizer, etc., may be included as needed.

[0167] As for the quinone diazide compound, a compound in which the sulfonic acid of naphthoquinone diazide is esterified to a compound having a phenolic hydroxyl group is preferred. Compounds having phenolic hydroxyl groups used herein 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, Methyleneris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (Trade name, Manufactured by Honshu Kagaku Kogyo 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 Yukizai Kogyo 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 E, Methylenebisphenol, BisP-AP (Trade name, It is preferable to exemplify a compound such as that of Honshu Kagaku High School Co., Ltd. in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced via an ester bond, but other compounds may also be used.

[0168] In addition, it is preferable that 50 mol% or more of the total functional groups of a compound having phenolic hydroxyl groups are substituted with quinone diazide. By using a quinone diazide compound substituted at 50 mol% or more, the affinity of the quinone diazide compound for an alkaline aqueous solution is reduced. As a result, the solubility of the resin composition in the unexposed portion in an alkaline aqueous solution is significantly reduced. Furthermore, the quinone diazide sulfonyl group is converted to indenecarboxylic acid by exposure, and a large dissolution rate of the photosensitive resin composition in the exposed portion in an alkaline aqueous solution can be obtained. That is, consequently, the ratio of the dissolution rates of the exposed portion and the unexposed portion of the composition is increased, thereby enabling the acquisition of a pattern with high resolution.

[0169] By including such a quinone diazide compound, a resin composition having positive photosensitive properties that are sensitive to the i-line (365 nm), h-line (405 nm), g-line (436 nm) of a general mercury lamp or to a broadband including them can be obtained. In addition, a resin composition with high sensitivity can be obtained by including only one type of component (D) or by including two or more types in combination.

[0170] Examples of quinone diazides include 5-naphthoquinone diazide sulfonyl groups, 4-naphthoquinone diazide sulfonyl groups, and those containing 4-naphthoquinone diazide sulfonyl groups and 5-naphthoquinone diazide sulfonyl groups in the same molecule.

[0171] As a naphthoquinone diazide sulfonyl ester compound, it is preferable to include a 5-naphthoquinone diazide sulfonyl ester compound (D-1). The (D-1) component has an extended absorption range up to the g-line region of a mercury lamp and is suitable for g-line exposure and full-length exposure. Additionally, upon curing, it reacts with component (A) or component (B) to form a cross-linked structure, thereby improving chemical resistance.

[0172] As for the naphthoquinone diazide sulfonyl ester compounds, it is preferable to have a 5-naphthoquinone diazide sulfonyl ester compound (D-1) and a 4-naphthoquinone diazide sulfonyl ester compound (D-2), with a content ratio of (D-2) / (D-1) = 0.3 to 3. The (D-2) component has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. In addition, since the acid generated by exposure is a strong acid, sulfonic acid, the alkali dissolution of the entire exposed area increases during development, thereby improving the pattern shape after development and heat treatment. Therefore, by setting the content ratio to (D-2) / (D-1) = 0.3 to 3, chemical resistance and the pattern shape after heat treatment can be achieved simultaneously.

[0173] Quinone diazide compounds can be synthesized by known methods through the esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. By using quinone diazide compounds, resolution, sensitivity, and residual film rate are further improved.

[0174] (D) The molecular weight of the component is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, more preferably 1,500 or less, based on the heat resistance, mechanical properties and adhesion of the film obtained by heat treatment.

[0175] (D) Among the components, sulfonium salts, phosphonium salts, and diazonium salts are preferred because they adequately stabilize the acidic components generated by exposure. Among these, sulfonium salts are preferred.

[0176] The content of component (D) is preferably 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (A). If the content of component (D) is 0.1 parts by mass or more and 100 parts by mass or less, it is possible to impart photosensitivity while maintaining the heat resistance, chemical resistance, and mechanical properties of the film after heat treatment.

[0177] When component (D) contains a quinone diazide compound, the content of component (D) is more preferably 1 part by mass or more and more preferably 3 parts by mass or more per 100 parts by mass of component (A). In addition, 100 parts by mass or less is more preferably and 80 parts by mass or less is more preferably. If the content 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 mechanical properties of the film after heat treatment.

[0178] When component (D) contains a sulfonium salt, a phosphonium salt, or a diazonium salt, the content of component (D) is more preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more, relative to 100 parts by mass of component (A). Additionally, 100 parts by mass or less is more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less. If the content is 0.1 parts by mass or more and 100 parts by mass or less, it is possible to impart photosensitivity while maintaining the heat resistance, chemical resistance, and mechanical properties of the film after heat treatment.

[0179] (D) When a photobase generator is included as a component, specific examples of photobase generators include amide compounds, ammonium salts, etc.

[0180] Examples of amide compounds include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N,N-dimethylcarbamate, 1-(anthraquinone-2yl)ethylimidazolecarboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine.

[0181] Examples of ammonium salts include 1,2-diisopropyl-3-(bis-dimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate, (Z)-{[bis(dimethylamino)methylene]amino}-N-cyclohexylamino)methanimium tetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, etc.

[0182] When a photobase generator is included as component (D), the content of component (D) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more, with respect to 100 parts by mass of component (A). If the content is within the above range, the sensitivity during exposure can be improved. Meanwhile, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. If the content is within the above range, the resolution after development can be improved.

[0183] (D) When a photopolymerization initiator is included as a component, the photopolymerization initiator is preferably, for example, a benzyl ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic keto ester-based photopolymerization initiator, a benzoic acid ester-based photopolymerization initiator, or a titanocene-based photopolymerization initiator. From the perspective of improving sensitivity during exposure, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, or benzophenone-based photopolymerization initiators are more preferred, and α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are even more preferred.

[0184] As α-aminoketone-based photopolymerization initiators, for example, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)-2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, Examples include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, and 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morphonyl)phenyl]-1-butanone.

[0185] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0186] As oxime ester-based photopolymerization initiators, for example, 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanol-1-(O-acetyl)oxime, Examples include 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolane-4-yl)methyloxy]benzoyl]-9H-carbazole-3-yl]ethanol-1-(O-acetyl)oxime or "Adeca Arcles" (registered trademark) NCI-831.

[0187] When a photopolymerization initiator is included as component (D), the content of component (D) in the resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more, per 100 parts by mass of component (A). If the content is within the above range, the sensitivity during exposure can be improved. Meanwhile, the content is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. If the content is within the above range, the resolution after development can be improved.

[0188] Others

[0189] The resin composition of the present invention may, if necessary, contain other components such as a radical polymerizable compound, an antioxidant, a solvent, a compound having a phenolic hydroxyl group, an adhesion improver, an adhesion improver, and a surfactant.

[0190] Method for manufacturing a resin composition

[0191] Next, a method for manufacturing the resin composition of the present invention will be described. For example, a resin composition can be obtained by mixing and dissolving each of the above components (A), (B), and (C), and, if necessary, component (D), a radical polymerizable compound, an antioxidant, a solvent, a compound having a phenolic hydroxyl group, an adhesion improver, an adhesion improver, a surfactant, etc.

[0192] Known methods for dissolution include heating or stirring.

[0193] The viscosity of the resin composition is preferably 2 to 5,000 mPa·s. By adjusting the solid content concentration so that the viscosity becomes 2 mPa·s or higher, it becomes easier to obtain a desired film thickness. On the other hand, if the viscosity is 5,000 mPa·s or lower, it becomes easier to obtain a coating film with high uniformity. A resin composition having such viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60 mass%. Here, solid content concentration refers to components other than solvents.

[0194] It is desirable to filter the obtained resin composition using a filtration filter to remove debris or particles. The materials for the filtration filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), but polyethylene or nylon is preferred.

[0195] Suzy Sheet

[0196] The resin sheet of the present invention is a resin sheet formed on a substrate using the resin composition. Specifically, it refers to a sheet obtained by applying the resin composition to a substrate and drying it.

[0197] A film such as polyethylene terephthalate (PET) can be used as the substrate for applying the resin composition. When the resin sheet is bonded to a substrate such as a silicon wafer and the substrate needs to be peeled off, it is preferable to use a substrate coated with a release agent such as silicone resin on its surface, as this allows the resin sheet and the substrate to be easily peeled off.

[0198] Method for manufacturing a hardened film

[0199] Next, the resin composition of the present invention, or the cured film of the present invention obtained by curing the resin sheet of the present invention, and the method for manufacturing the same will be described.

[0200] Hereinafter, the term "resin film" refers to a film obtained by applying the resin composition of the present invention to a substrate and drying it. Additionally, the term "cured film" refers to a film obtained by curing a resin film or a resin sheet.

[0201] A method for manufacturing a cured film according to the present invention preferably comprises a process of applying the resin composition to a substrate or laminating a resin sheet to a substrate and then drying to form a resin film, an exposure process of exposing the dried resin film, a development process of developing the exposed resin film, and a heat treatment process of heat-treating the developed resin film.

[0202] First, the resin composition of the present invention is applied to a substrate to obtain a coating film of the resin composition. As a substrate, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and substrates on which circuit constituent materials are arranged are used, but are not limited to these. As a coating method, spin coating, slit coating, dip coating, spray coating, printing, etc. are used. In addition, the thickness of the coating film varies depending on the coating method, the solid content concentration of the composition, viscosity, etc., but is typically applied such that the film thickness after drying is 0.1 to 150 μm.

[0203] Prior to coating, the substrate to which the resin composition is to be coated may be pretreated with the adhesion improver described above. For example, the substrate surface may be treated by spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment using a solution in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipoyl acid at a concentration of 0.5 to 20 mass%. After treating the substrate surface, vacuum drying treatment may be performed as needed. Additionally, the reaction between the substrate and the adhesion improver may be carried out by heat treatment at 50°C to 280°C.

[0204] Next, the coating film of the resin composition is dried to obtain a resin film. It is preferable to dry the film using an oven, hot plate, infrared light, etc., at a temperature range of 50°C to 140°C for 1 minute to several hours.

[0205] Meanwhile, when using a resin sheet formed from the resin composition of the present invention, if the resin sheet has a protective film, the protective film is peeled off, and the resin sheet and the substrate are placed facing each other and bonded by heat pressing (the act of placing the resin sheet and the substrate facing each other and bonding by heat pressing may also be described as laminating the resin sheet to the substrate). Subsequently, the resin sheet laminated to the substrate is dried in the same manner as when obtaining the resin film to form a resin film. The resin sheet can be obtained by applying and drying the resin composition of the present invention onto a support film composed of a releaseable substrate such as polyethylene terephthalate.

[0206] Thermal compression can be performed by heat press treatment, heat lamination treatment, heat vacuum lamination treatment, etc. The bonding temperature is preferably 40°C or higher due to the adhesion and embedding properties to the substrate. In addition, if the resin sheet is photosensitive, the bonding temperature is preferably 140°C or lower to prevent the resin sheet from curing during bonding and to prevent a decrease in the resolution of pattern formation during the exposure and development processes.

[0207] In the photolithography process, a chemical line is irradiated onto a photosensitive resin film through a mask having a desired pattern. Chemical lines used for exposure include ultraviolet rays, visible light, electron beams, and X-rays, but in the present invention, it is preferable to use general exposure wavelengths such as g-lines (436 nm), h-lines (405 nm), or i-lines (365 nm). In the case of a non-photosensitive resin film, the chemical line is irradiated after forming a photoresist following the formation of the resin film.

[0208] Next, the photosensitive resin film that has been exposed is developed. As a developer, an aqueous solution of an alkaline compound such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc., is preferred. In addition, depending on the case, one or more types of polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butylolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methylisobutyl ketone may be added to these alkaline aqueous solutions. It is common practice to rinse with water after development. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

[0209] The resin film obtained in this manner is heated to carry out a thermal crosslinking reaction, thereby obtaining the cured film of the present invention. The cured film has improved heat resistance and chemical resistance due to crosslinking. This heat treatment may be performed by increasing the temperature in stages or by increasing the temperature continuously. It is preferable to perform the heat treatment for 5 minutes to 5 hours. As an example, a heat treatment may be performed at 100°C for 30 minutes, followed by an additional heat treatment at 230°C for 60 minutes. The heat treatment conditions are preferably 140°C or higher and 400°C or lower. To carry out the thermal crosslinking reaction, the heat treatment conditions are preferably 140°C or higher, and more preferably 160°C or higher. Furthermore, to provide an excellent cured film and to improve the reliability of semiconductor devices or display devices, the heat treatment conditions are preferably 300°C or lower, and more preferably 250°C or lower.

[0210] The cured film of the present invention obtained in this way preferably has an opening pattern, and the angle of the inclined side in the cross-section of the opening pattern is 40° or more and 80° or less.

[0211] FIG. 3 shows a front cross-sectional view of the opening pattern of the hardened film. In FIG. 3, the angle of the inclined side (14) is 15 for the opening pattern formed in the hardened film (3). Additionally, the inclined side is formed by connecting the upper opening pattern and the lower opening pattern in a straight line.

[0212] By setting the angle of the inclined side in the cross-section of the opening pattern of the cured film to this range, the semiconductor device or display device described later to which the cured film is applied is less likely to cause defects such as short circuits or wiring defects, and thus has excellent reliability.

[0213] Semiconductor Device

[0214] The resin composition of the present invention, or the cured film of the present invention obtained by curing the resin sheet of the present invention, can be used in electronic components such as known semiconductor devices. That is, the semiconductor device of the present invention has the cured film of the present invention. The semiconductor device of the present invention has metal wiring and an insulating film, and has the cured film of the present invention as an insulating film. A semiconductor device generally refers to a device that includes semiconductor elements or integrated circuits incorporating such elements as components. The semiconductor device of the present invention includes not only a device that includes semiconductor elements but also components for semiconductor devices such as wiring boards. Furthermore, a semiconductor package in which semiconductor elements, etc. are protected by a sealing resin and also have the function of being electrically connected to the outside is also included in the semiconductor device of the present invention. Specifically, the cured film of the present invention is suitable for use as a passivation film for semiconductors, a protective film for semiconductor elements, an interlayer insulating film for multilayer wiring for high-density packaging, etc.

[0215] In particular, recent semiconductor devices have become mainstream as electrodes, metal wiring, and vamps made of gold, silver, copper, nickel, aluminum, etc., due to the further miniaturization of the electrodes of semiconductor devices or the metal wiring of substrates. During the formation of these devices, the metal wiring or barrier metal etching process and the resist pattern formation process come into contact with many chemicals, such as flux and stripper for removing photoresist. When a cured film made of the resin composition or resin sheet of the present invention is used as a protective film for such electrodes or metal wiring, it is particularly advantageous to use it because it has high resistance to those chemicals. Furthermore, copper wiring may undergo oxidation treatment during the manufacturing process. Even in such cases, the cured film of the present invention can be advantageously used.

[0216] Preferred examples of a semiconductor device having the resin composition of the present invention, or a cured film of the present invention obtained by curing the resin sheet of the present invention (hereinafter referred to as a cured film made of the resin composition or resin sheet of the present invention) include, for example, a logic device such as a CPU or GPU described in International Publication No. 2018 / 066395, a semiconductor device having a vamp such as a polymer memory (Polymer Ferroelectric RAM: PFRAM) or phase change memory (Phase Change RAM: PCRAM, or Ovonic Unified Memory: OUM) which is promising as a next-generation memory, a fan-out wafer level package (fan-out WLP) or a fan-out panel level package (fan-out PLP), a coil component of an inductor device, a mini LED with a chip size of 100 to 700 μm, or a micro LED with a chip size of 100 μm or less.

[0217] In the case of a semiconductor device having a vamp, a fan-out wafer-level package (fan-out WLP) or a fan-out panel-level package (fan-out PLP), or a coil component of an inductor device, a cured film made of the resin composition or resin sheet of the present invention may be formed as an insulating film, and then metal wiring (so-called redistribution) may be further formed thereon. By repeating the above process, a multilayer wiring structure in which two or more layers of redistribution are separated by an insulating film made of the cured resin composition or resin sheet of the present invention can be formed. The insulating film separating these redistributions is called an interlayer insulating film. At this time, the formed insulating film comes into contact with various chemical solutions multiple times, but since the insulating film made of the cured resin composition or resin sheet of the present invention has excellent adhesion and chemical resistance, a good multilayer wiring structure can be formed. In addition, when the resin composition or resin sheet of the present invention has photosensitive properties, it exhibits an excellent tapered shape after curing, thereby improving the degree of freedom in the layout design of copper wiring when forming multilayer metal wiring; thus, it can be particularly preferably used as a protective film for multilayer metal wiring. Although there is no upper limit on the number of layers in the multilayer wiring structure, 10 layers or fewer are commonly used.

[0218] In fan-out WLP or fan-out PLP, the rewiring is becoming finer. The cured film of the present invention is suitable for use in fine rewiring because it has high metal adhesion even to metal wiring where the width of the metal wiring and the spacing between adjacent metal wirings are 5 μm or less. Here, the width of the metal wiring and the spacing between adjacent metal wirings are 5 μm or less means that the width of the metal wiring is 5 μm or less, and the spacing between adjacent metal wirings is also 5 μm or less.

[0219] In a fan-out WLP or fan-out PLP having such a microstructure, a multilayer stacked structure in which a plurality of redistribution layers are stacked is provided, and among adjacent redistribution layers, the width of the metal wiring in the redistribution layer closer to the semiconductor chip and the spacing between adjacent metal wirings are preferably equal to or narrower than the width of the metal wiring in the redistribution layer farther from the semiconductor chip and the spacing between adjacent metal wirings. Here, a redistribution layer refers to a layer consisting of a set of redistributions and an interlayer insulating film formed thereon, in a multilayer wiring structure in which a plurality of redistributions are separated by a plurality of interlayer insulating films. Additionally, there are cases where the redistribution layer consists of only one layer. Furthermore, the statement that the width of the metal wiring in the redistribution layer and the spacing between adjacent metal wirings are equal or narrower means that the width of the metal wiring in the redistribution layer closer to the semiconductor chip is equal or narrower compared to the width of the metal wiring in the redistribution layer farther from the semiconductor chip, and also that the spacing between adjacent metal wirings in the redistribution layer closer to the semiconductor chip is equal or narrower compared to the spacing between adjacent metal wirings in the redistribution layer farther from the semiconductor chip.

[0220] In addition, in these structures, it is desirable that the thickness of the interlayer insulating film of the redistribution layer closer to the semiconductor chip among adjacent redistribution layers be the same as or narrower than the thickness of the interlayer insulating film of the redistribution layer farther from the semiconductor chip.

[0221] <Display device>

[0222] The resin composition or the cured film formed by curing the resin sheet of the present invention is suitable for use in a display device comprising a first electrode formed on a substrate and a second electrode formed opposite to the first electrode, specifically, for example, a display device using an LCD, ECD, ELD, or organic EL.

[0223] The organic EL display device of the present invention is an organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, and it is preferable that the planarization layer or the insulating layer comprises the cured film of the present invention.

[0224] In addition, a display device having at least metal wiring, a cured film of the present invention, and a plurality of light-emitting elements is preferably configured such that the light-emitting element has a pair of electrode terminals on one side, the pair of electrode terminals are connected to a plurality of metal wirings extending into the cured film, and the plurality of metal wirings maintain electrical insulation by the cured film.

[0225] Figure 1 is described as an example of the above-mentioned display device.

[0226] In FIG. 1, the display device (1) places a plurality of light-emitting elements (2) on a counter substrate (5) and places a cured film (3) on the light-emitting elements (2). The surface of the light-emitting elements may be not only the surface of the light-emitting elements but also a supporting substrate or the upper side of the light-emitting elements. In the form shown in FIG. 1, a configuration is illustrated in which a plurality of cured films (3) are further stacked on top of a cured film (3) that is formed to be in contact with at least a part of the light-emitting elements (2) to form a total of three layers, but this is not limited thereto, and the cured film (3) may also be a single layer. The light-emitting elements (2) are provided with a pair of electrode terminals (6) on a surface opposite to the surface in contact with the counter substrate (5), and each electrode terminal (6) is connected to a metal wiring (4) that extends into the cured film (3). Additionally, a plurality of metal wires (4) extending into the hardened film (3) are covered by the hardened film (3), and since the hardened film (3) also functions as an insulating film, the configuration is configured to maintain electrical insulation. Furthermore, the light-emitting element (2) is electrically connected to a driving element (8) attached to a light-emitting element driving substrate (7) formed at a position opposite to the opposing substrate (5) through metal wires (4 or 4c), thereby allowing the light emission of the light-emitting element (2) to be controlled. Additionally, the light-emitting element driving substrate (7) is electrically connected to the metal wires (4) through, for example, a solder vamp (10). Furthermore, a barrier metal (9) may be placed to prevent the diffusion of metals such as the metal wires (4). Also, in the following drawings, the metal wires (4c) may penetrate the light-emitting element driving substrate (7) and be connected to the driving element (8).

[0227] The above cured film (3) is a cured film formed by curing the resin composition or resin sheet of the present invention.

[0228] The material of the metal wiring (4) is not particularly limited and any known material can be used. Examples include gold, silver, copper, aluminum, nickel, etc., and copper is preferred.

[0229] As a separate embodiment of the above-described display device, as shown in FIG. 4, a configuration is illustrated in which a cured film (16) is formed to be in contact with at least a part of the light-emitting element (2) with respect to the display device of FIG. 1. The cured film (16) arranged to be in contact with at least a part of the light-emitting element (2) may be composed of a cured film formed by curing the resin composition or resin sheet of the present invention, or it may be composed of a material other than a cured film formed by curing the resin composition or resin sheet of the present invention, or a known material such as epoxy resin, silicone resin, fluoropolymer resin may be used.

[0230] In addition, in the present invention, it is preferable that the total thickness of the cured film is 5㎛ to 100㎛.

[0231] By having a total thickness of 5㎛ to 100㎛ of the cured film, it is possible to reduce the size of the display device itself having the light-emitting element, suppress wiring defects such as short circuits in wiring due to short wiring distances, suppress loss, and improve high-speed response.

[0232] The total thickness of the cured film refers to the total thickness of a continuous layer of cured films in which at least a portion of one cured film is in contact with another cured film. For example, in the case where multiple cured films (3) are stacked as shown in Fig. 1 above, the area indicated by 12 in Fig. 1 is the total thickness of the layer of cured films. The total thickness is preferably 7 to 70 μm, and more preferably 8 to 60 μm. If it is less than 5 μm, there is a concern about wiring defects such as short circuits in the wiring because the protection of the metal wiring is insufficient, and if it exceeds 100 μm, there may be a case of failure in suppressing wiring defects such as short circuits in the wiring due to the reduction of the display device itself and the reduction of wiring distance, as well as in suppressing loss and improving high-speed response.

[0233] In addition, when multiple cured films are stacked, it is preferable that the number of cured film layers be between 2 and 10.

[0234] From the perspective of arranging multiple light-emitting elements, it is preferable to have one or more layers of cured film, and by having two or more layers, the number of metal wires that can be connected to the light-emitting elements can be increased, so multiple light-emitting elements can be arranged. Also, from the perspective of suppressing wiring defects such as short circuits in wiring due to package reduction or wiring short distances, reducing losses, and improving high-speed response, it is preferable to have 10 or fewer layers.

[0235] With this configuration, minute light-emitting elements can be applied, and high-density mounting of multiple light-emitting elements becomes possible, thereby enabling a display device having high-resolution light-emitting elements in a wide range of sizes. Furthermore, it becomes possible to form fine metal wiring, and since the number of wirings that can be formed per unit area increases, the overall thickness of the cured film can be reduced. This enables the display device itself to be smaller, and allows for the suppression of wiring defects such as short circuits and loss reduction due to shorter wiring distances, as well as the improvement of high-speed responsiveness.

[0236] From the perspective of applying a small light-emitting element or high-density mounting of the light-emitting element, the maximum length of the bottom portion of the metal wiring is preferably 2 to 15 μm, more preferably 2 to 10 μm, and even more preferably 2 to 5 μm. If it is less than 2 μm, a poor connection with the light-emitting element (2) may occur, and if it exceeds 20 μm, it may cause harm to the application of the small light-emitting element or high-density mounting.

[0237] In addition, it is preferable that the light-emitting element is an LED with a side length of 5㎛ or more and 700㎛ or less, and it is even more preferable that the light-emitting element is an LED with a side length of 5㎛ or more and 100㎛ or less.

[0238] In addition, in the present invention, a partition may be formed between a plurality of the light-emitting elements, the partition being composed of a cured film having a thickness greater than or equal to the thickness of the light-emitting elements and comprising a resin composition including the (A) resin.

[0239] As shown in FIG. 2 as a separate embodiment, it is preferable to have a repeating pattern according to the number of pixels of a display device (1) having a light-emitting element (2), that is, a partition (11) between or around each light-emitting element (2). This configuration is preferable because it facilitates bonding with an opposing substrate (5).

[0240] The thickness of the partition wall is preferably greater than the thickness of each light-emitting element, and specifically, 5㎛ to 120㎛ is preferred.

[0241] In addition, the partition wall may be a cured film formed by curing the resin composition or resin sheet of the present invention, or it may be composed of other materials, and known materials such as epoxy resin, (meth)acrylic polymer, polyurethane, polyester, polyolefin, and polysiloxane may be used.

[0242] In addition, it is preferable to arrange a partition wall having a thickness greater than or equal to the thickness of the light-emitting element between the plurality of the light-emitting elements in the cured film covering the light-emitting elements.

[0243] (Example)

[0244] The present invention will be explained below with reference to examples, but the present invention is not limited by these examples. In addition, the evaluation of the resin composition or resin sheet in the examples was performed by the following method. In addition, for the evaluation, a resin composition (hereinafter referred to as varnish) that had been filtered in advance through a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Company) was used.

[0245] <Evaluation of Resin Compositions Not Photosensitive>

[0246] (1) Evaluation of the opening pattern shape of a cured film made of a resin composition that does not have photosensitive properties

[0247] A varnish was prepared and applied to an 8-inch silicon wafer using the spin coat method with the coating / developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) to produce a prebaked film, such that the film thickness after heat treatment was 7㎛. The prebaking was performed at 110°C for 3 minutes. Subsequently, a positive-type photoresist OFPR-800 (manufactured by Tokyo Okaz) was applied to the prebaked film, and the prebaking was performed at 100°C for 10 minutes. Next, an i-line stepper (Nikon Inc., NSR-2205i14) was used to expose the film at exposure amounts of 100 to 800 mJ / cm². The size of the circular pattern used for exposure was 30㎛. After exposure, a 2.38 mass% aqueous tetramethylammonium (TMAH) solution (manufactured by Tama Kagaku Kogyo) was used to develop the film under conditions where the change in film thickness of the unexposed area before and after development was 1.5 μm, followed by rinsing with pure water and drying by blowing to obtain a pattern forming film. In addition, the film thickness after pre-baking and after development was measured using a Dainippon Screen Seizo Co., Ltd. optical interferometric film thickness measuring device Lambda Ace STM-602 with a refractive index of 1.629.

[0248] Next, the temperature was increased from 50°C to 100°C at a rate of 3.5°C / min, and heat treatment was continued at 100°C for 30 minutes. After that, the temperature was increased to 160°C at a rate of 3.5°C / min, and baking was continued at 160°C for 10 minutes. Then, the photoresist film was removed by immersing in stripping solution 106 (Tokyo Okaze) for 3 minutes and rinsing with pure water.

[0249] Subsequently, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised from 50°C to 100°C at a rate of 3.5°C / min under a nitrogen stream with an oxygen concentration of 20 ppm or less, and a heat treatment was subsequently performed at 100°C for 30 minutes. After that, the temperature was raised at a rate of 3.5°C / min to 200°C, 230°C, or 250°C, which are the curing temperatures listed in Table 3, and a heat treatment was subsequently performed for 1 hour at the curing temperature after the temperature increase listed in Table 3 to cure the pattern forming film and obtain a cured film.

[0250] After withdrawing the wafer at a temperature of 50°C or lower, the wafer was cut, and a 5 μm circular pattern cross-sectional shape was observed and measured using a scanning electron microscope S-4800 (Hitachi Hitech). In addition, the angle of the inclined side was calculated by connecting the upper opening pattern and the lower opening pattern with a straight line, with the inclined side being the angle of the inclined side.

[0251] As a result, if the angle of the inclined side was between 40° and 80°, it was evaluated as good (2), and if it was between 40° or 80° or more, it was evaluated as poor (1).

[0252] (2) Evaluation of chemical resistance of a resin composition that does not have photosensitivity

[0253] A varnish was prepared and applied to an 8-inch silicon wafer using the spin coat method with the coating / developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) to produce a prebaked film, such that the film thickness after heat treatment was 7 μm. The prebaking was performed at 110°C for 3 minutes. Subsequently, using a 2.38 mass% aqueous solution of tetramethylammonium (TMAH) (manufactured by Tama Kagaku Kogyo), the film was developed under conditions where the change in film thickness of the unexposed area before and after development was 1.5 μm. The film was then rinsed with pure water and dried by blowing to obtain a developed resin film.

[0254] After that, the coating film was heated using an inert oven (manufactured by Koyo Thermo System Co., Ltd., CLH-21CD-S) under a nitrogen stream at an oxygen concentration of 20 ppm or less, increasing the temperature from 50°C to 100°C at a rate of 3.5°C / min, and then heat treatment was performed at 100°C for 30 minutes. Subsequently, the temperature was increased at a rate of 3.5°C / min to 200°C, 230°C, or 250°C, which are the curing temperatures listed in Table 3, and then heat treatment was performed for 1 hour at the curing temperature after the temperature increase listed in Table 3 to cure the coating film and obtain a cured film. In addition, the film thickness of the coating film after pre-baking and after development was measured using the Lambda Ace STM-602 optical interferometric film thickness measuring device manufactured by Dainippon Screen Seizo Co., Ltd. with a refractive index of 1.629, and the film thickness of the cured film was measured with a refractive index of 1.629.

[0255] A silicon wafer was withdrawn at a temperature of 50°C or lower, and the obtained cured film was immersed in a stripper composed of NMP / DMSO / ethanolamine = 70 / 20 / 10 and treated at 70°C for 30 minutes. Afterward, the presence or absence of peeling or leaching was observed, and the rate of change in film thickness was measured.

[0256] As a result, if the rate of change in film thickness before and after immersion was 5% or less, it was evaluated as very good (3); if the rate of change in film thickness exceeded 5% but was 10% or less, it was evaluated as good (2); and if the rate of change in film thickness exceeded 10% or peeling or leaching was observed, it was evaluated as poor (1). A smaller value for the rate of change in film thickness indicates better chemical resistance.

[0257] (3) Evaluation of HAST resistance of a non-photosensitive resin composition on a copper wiring substrate. In performing a peeling evaluation on copper wiring, the following evaluation substrate was prepared. Copper wiring with a thickness of 3 μm, a width of 50 μm, and a wiring spacing of 100 μm was formed on an 8-inch silicon wafer. This was used as the evaluation substrate.

[0258] A varnish was applied to the above-mentioned evaluation substrate using the spin coating method with the coating / developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) and pre-baked so that the film thickness after heat treatment was 7 μm, thereby producing a pre-baked film. The pre-baking was performed at 110°C for 3 minutes. Subsequently, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised from 50°C to 100°C at a rate of 3.5°C / min under a nitrogen air stream with an oxygen concentration of 20 ppm or less, and heat treatment was continued at 100°C for 30 minutes. Afterward, the temperature was raised at a rate of 3.5°C / min to 200°C, 230°C, or 250°C, which are the curing temperatures listed in Table 3, and heat treatment was continued for 1 hour at the curing temperature after the temperature increase listed in Table 3 to cure the pre-baked film and obtain a cured film. An evaluation substrate (hereinafter referred to as the sample) was withdrawn from a place where the temperature was 50℃ or lower.

[0259] Next, the sample was placed into a HAST device and treated for 168 hours at a temperature of 130°C and a humidity of 85%. Afterward, the sample was removed, and to observe delamination between the resin composition and the copper wiring, the sample was cut and cross-sectionally observed at a magnification of 50,000x using a scanning electron microscope Versa 3D Dual Beam (manufactured by FEI Co., Ltd.) attached to a converged ion beam processing device.

[0260] As a result, the condition where no delamination was observed between the resin composition and the copper wiring was evaluated as very good (2), the condition where some defects such as delamination or voids were observed was evaluated as slightly poor (1), and the condition where defects such as delamination or voids were observed throughout was evaluated as poor (0). The less delamination or voids there are, the better the HAST resistance.

[0261] <Evaluation of Photosensitive Resin Compositions>

[0262] (4) Evaluation of the opening pattern shape of a cured film made of a photosensitive resin composition

[0263] A varnish was prepared and applied to an 8-inch silicon wafer using the spin coat method with the coating / developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) to produce a prebaked film, such that the film thickness after heat treatment was 7 μm. The prebaking was performed at 110°C for 3 minutes. Subsequently, an i-line stepper (Nikon Inc., NSR-2205i14) was used to expose the wafer with an exposure amount of 100 to 800 mJ / cm². The size of the circular pattern used for exposure was 5 μm. After exposure, a 2.38 mass% aqueous tetramethylammonium (TMAH) solution (manufactured by Tama Kagaku Kogyo) was used to develop the wafer under conditions where the change in film thickness in the unexposed area before and after development was 1.5 μm. Subsequently, the wafer was rinsed with pure water and diffusion dried to obtain a pattern-forming film. In addition, the film thickness after prebaking and after development was measured using the Lambda Ace STM-602 optical interferometric film thickness measuring device manufactured by Dainippon Screen Seizo Co., Ltd. with a refractive index of 1.629.

[0264] After development, an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) was used, and under a nitrogen stream, the temperature was raised from 50°C to 100°C at a rate of 3.5°C / min with an oxygen concentration of 20 ppm or less, and a heat treatment was subsequently performed at 100°C for 30 minutes. After that, the temperature was raised at a rate of 3.5°C / min to 200°C, 230°C, or 250°C, which are the curing temperatures listed in Table 4, and a heat treatment was subsequently performed for 1 hour at the curing temperature after the temperature increase listed in Table 4 to cure the pattern forming film and obtain a cured film.

[0265] After withdrawing the wafer at a temperature of 50°C or lower, the wafer was cut, and a 5 μm circular pattern cross-sectional shape was observed and measured using a scanning electron microscope S-4800 (Hitachi Hitech). In addition, the angle of the inclined side was calculated by connecting the upper opening pattern and the lower opening pattern with a straight line, with the inclined side being the angle of the inclined side.

[0266] As a result, if the angle of the inclined side was 40° or more and 80° or less, it was evaluated as good as 2, and if it was 40° or less or 80° or more, it was evaluated as poor as 1.

[0267] (5) Evaluation of chemical resistance of photosensitive resin composition

[0268] Except for what is shown in Table 4, it is the same as (2) above.

[0269] (6) HAST resistance evaluation of a photosensitive resin composition on a copper wiring substrate

[0270] Except for what is shown in Table 4, it is the same as (3) above.

[0271] <Synthesization Example 1: Synthesis of a Hydroxyl Group-Containing Diamine Compound>

[0272] 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Kasei Co., Ltd.), and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) dissolved in 100 mL of acetone was added dropwise to this. After the addition was finished, the mixture was stirred at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered and separated, and vacuum dried at 50°C.

[0273] 30g of the obtained white solid was placed in a 300mL stainless steel autoclave and dispersed in 250mL of methylcellulose, and 2g of 5% palladium-carbon (manufactured by Wako Junyaku Co., Ltd.) was added. Hydrogen was introduced into the balloon, and a reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated when it was confirmed that the balloon did not contract further. After the reaction was terminated, the palladium compound acting as a catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

[0274]

[0275] <Synthesization Example 2: Synthesis of Phenol Trinucleus>

[0276] 3.2 g (30 ml) of m-cresol and 1.2 g (10 ml) of p-hydroxybenzaldehyde were added to a 100 mL two-necked flask equipped with a cooling tube and a thermometer, and dissolved in 10 mL of 2-ethoxyethanol. While cooling in an ice bath, 1 mL of sulfuric acid was added, and the reaction was carried out by heating and stirring at 100°C for 2 hours. After the reaction, the resulting solution was redeposited with water to obtain a crude product. The crude product was redeposited in acetone and again redeposited with water; the resulting product was filtered, separated, and vacuum dried to obtain a phenol trinucleus compound represented by the following formula.

[0277]

[0278] <Synthesization Example 3: Synthesis of Phenol Trinucleus>

[0279] 3.2 g (30 ml) of m-cresol and 1.4 g (10 ml) of p-hydroxyacetophenone were added to a 100 mL two-necked flask equipped with a cooling tube and a thermometer, and dissolved in 10 mL of 2-ethoxyethanol. While cooling in an ice bath, 1 mL of sulfuric acid was added, and the reaction was carried out by heating and stirring at 100°C for 2 hours. After the reaction, the resulting solution was redeposited with water to obtain a crude product. The crude product was redeposited in acetone and again redeposited with water; the resulting product was filtered, separated, and vacuum dried to obtain a phenol trinucleus compound represented by the following formula.

[0280]

[0281] <Synthesization Example 4 Synthesis of Polybenzoxazole Precursor (A-1)>

[0282] Under a dry nitrogen stream, 1.5 g (0.0075 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as 4,4'-DAE), 12.8 g (0.035 mol) of BAHF, and 5.0 g (0.0050 mol) of RT-1000 (manufactured by HUNTSMAN Inc.) were dissolved in 100 g of NMP. To this, diimidazole dodecanoate (7.4 g, 0.023 mol) and PBOM (8.1 g, 0.023 mol) were added together with 25 g of NMP, and the mixture was reacted at 85°C for 3 hours. Subsequently, 0.6 g (0.0025 mol) of SiDA, 0.8 g (0.0025 mol) of ODPA, and 0.8 g (0.0050 mol) of NA were added together with 25 g of NMP, and the mixture was reacted at 85°C for 1 hour. After the reaction was finished, the mixture was cooled to room temperature, and 13.2 g (0.25 mol) of acetic acid was added along with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour. After stirring was finished, the solution was added to 1.5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, dried in a 50°C air-dryer for 3 days, and a powder of a polybenzoxazole precursor (A-1) was obtained.

[0283] <Synthesization Example 5 Synthesis of Polybenzoxazole Precursor (A-2)>

[0284] 27.5 g (0.075 mol) of BAHF was dissolved in 257 g of NMP under a dry nitrogen stream. To this, 17.2 g (0.048 mol) of PBOM was added together with 20 g of NMP, and the mixture was reacted at 85°C for 3 hours. Subsequently, 20.0 g (0.02 mol) of RT-1000 (manufactured by HUNTSMAN Inc.), 1.2 g (0.005 mol) of SiDA, and 14.3 g (0.04 mol) of PBOM were added together with 50 g of NMP, and the mixture was reacted at 85°C for 1 hour. Additionally, 3.9 g (0.024 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added together with 10 g of NMP as a terminal sealant, and the mixture was reacted at 85°C for 30 minutes. After the reaction was finished, the mixture was cooled to room temperature, and 52.8 g (0.50 mol) of acetic acid was added along with 87 g of NMP, and the mixture was stirred at room temperature for 1 hour. After stirring was finished, the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, dried in a 50°C air-dryer for 3 days, and a powder of a polybenzoxazole precursor (A-2) was obtained.

[0285] <Synthetic Example 6 Synthesis of Polyimide Precursor (A-3)>

[0286] Under a dry nitrogen stream, 51.9 g (0.086 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1.0 g (0.004 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were dissolved in 200 g of NMP. To this, 31.0 g (0.10 mol) of 4,4'-oxydiphthalic anhydride (hereinafter referred to as ODPA) was added, and the mixture was stirred at 40°C for 2 hours. Then, 1.1 g (0.01 mol) of 3-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added as a terminal sealant along with 10 g of NMP, and the mixture was reacted at 40°C for 1 hour. After that, 7.1 g (0.06 mol) of dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Corporation, hereinafter referred to as DFA) was added dropwise to a solution diluted in 5 g of NMP. After adding, stirring was continued at 40°C for 2 hours. After stirring was finished, the solution was added to 2 L of water, and the precipitate of the polymer solid was collected by filtration. Additionally, the mixture was washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain a polyimide precursor (A-3).

[0287] <Synthetic Example 7 Synthesis of Polyimide Precursor (A-4)>

[0288] Under a dry nitrogen stream, 41.1 g (0.068 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1, 18.0 g (0.018 mol) of a diamine containing a structure of propylene oxide and tetramethylene ether glycol (RT-1000, manufactured by HUNTSMAN, Inc.), and 1.0 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. 31.0 g (0.10 mol) of ODPA was added to this, and the mixture was stirred at 40°C for 2 hours. Then, 1.1 g (0.01 mol) of 3-aminophenol was added as a terminal sealant along with 10 g of NMP, and the mixture was reacted at 40°C for 1 hour. Afterward, a solution of 6.0 g (0.05 mol) of DFA (manufactured by Mitsubishi Rayon, Inc.) diluted with 5 g of NMP was added dropwise. After dropping, stirring was continued at 40°C for 2 hours. After stirring was finished, the solution was added to 2 L of water, and the precipitate of the polymer solid was collected by filtration. Additionally, the solution was washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain a polyimide precursor (A-4).

[0289] <Synthetic Example 8 Synthesis of Polyimide (A-5)>

[0290] Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.2 g (0.005 mol) of SiDA, and 3.3 g (0.03 mol) of 3-aminophenol as a terminal sealant were dissolved in 80 g of NMP. To this, 31.2 g (0.1 mol) of ODPA was added along with 20 g of NMP, reacted at 60°C for 1 hour, and then stirred at 180°C for 4 hours. After stirring was finished, the solution was added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a polyimide (A-5) powder.

[0291] <Synthesization Example 9 Synthesis of Phenolic Resin (B-1)>

[0292] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 34.0 g (0.32 mol) of benzaldehyde, 90.4 g (0.74 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-1). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

[0293] <Synthesization Example 10 Synthesis of Phenolic Resin (B-2)>

[0294] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 11.7 g (0.11 mol) of benzaldehyde, 116.0 g (0.95 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added, and five liquid washes were performed. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-2). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 90:10.

[0295] <Synthesization Example 11 Synthesis of Phenolic Resin (B-3)>

[0296] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 44.6 g (0.42 mol) of benzaldehyde, 76.9 g (0.63 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-3). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 60:40.

[0297] <Synthesization Example 12 Synthesis of Phenolic Resin (B-4)>

[0298] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 128.2 g (1.05 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-4). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 100:0.

[0299] <Synthesization Example 13 Synthesis of Phenolic Resin (B-5)>

[0300] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 56.2 g (0.53 mol) of benzaldehyde, 64.7 g (0.53 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-5). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 50:50.

[0301] <Synthesization Example 14 Synthesis of Phenolic Resin (B-6)>

[0302] Under a dry nitrogen stream, 108.1 g (1.0 mol) of m-cresol, 38.4 g (0.32 mol) of acetophenone, 100.8 g (0.74 mol) of 4-hydroxyacetophenone, 200 g of 2-ethoxyethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted at 120°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-6). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

[0303] <Synthesization Example 15 Synthesis of Phenolic Resin (B-7)>

[0304] Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 34.0 g (0.32 mol) of benzaldehyde, 90.4 g (0.74 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform liquid washing five times. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-7). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

[0305] <Synthesization Example 16 Synthesis of Phenolic Resin (B-8)>

[0306] Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 11.7 g (0.11 mol) of benzaldehyde, 116.0 g (0.95 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-8). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 90:10.

[0307] <Synthesization Example 17 Synthesis of Phenolic Resin (B-9)>

[0308] Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 44.6 g (0.42 mol) of benzaldehyde, 76.9 g (0.63 mol) of salicylaldehyde, 200 g of ethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted for 18 hours under reflux at 65°C. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-9). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 60:40.

[0309] <Synthesization Example 18 Synthesis of Phenolic Resin (B-10)>

[0310] Under a dry nitrogen stream, 320.4 g (1.0 mol) of the trinuclear phenol compound obtained in Synthesis Example 2, 38.4 g (0.32 mol) of acetophenone, 100.8 g (0.74 mol) of 4-hydroxyacetophenone, 200 g of 2-ethoxyethanol, and 8.6 g (0.05 mol) of p-toluenesulfonic acid were introduced into a reaction vessel and reacted at 120°C for 18 hours. After neutralizing the reaction system with caustic soda, methyl isobutyl ketone and water were added to perform five rounds of liquid washing. Methyl isobutyl ketone was removed by vacuum distillation at 100°C using an evaporator to obtain phenol resin (B-10). The ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 70:30.

[0311] <Synthesization Example 19 Synthesis of Phenolic Resin (B-11)>

[0312] Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 37 wt% of 75.5 g of an aqueous formaldehyde solution (0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were added to a flask, immersed in an oil bath, and a polycondensation reaction was carried out for 4 hours while refluxing the reaction solution. Afterward, the temperature of the oil bath was increased over 3 hours, and then the pressure inside the flask was reduced to 40–67 hPa to remove volatile matter, and cooled to room temperature to obtain a polymer solid of phenol resin (B-11). The weight average molecular weight obtained by GPC was 3500.

[0313] <Synthesization Example 20 Synthesis of a Photosensitive Agent (Quinone Diazide Compound) (D-1)>

[0314] 21.2 g (0.05 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol (manufactured by Honshu Kagaku Kogyo Co., Ltd., hereinafter referred to as TrisP-PA) and 37.5 g (0.14 mol) of 5-naphthoquinone diazide sulfonic acid chloride (manufactured by Toyo Kosei Co., Ltd., NAC-5) were dissolved in 450 g of γ-butylolactone at room temperature under a dry nitrogen stream. To this, 12.7 g of triethylamine mixed with 50 g of γ-butylolactone was added dropwise so that the temperature in the system did not exceed 35°C. After adding, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. Subsequently, the precipitated precipitate was collected by filtration and washed with 1 L of 1% hydrochloric acid solution. Afterwards, it was washed two more times with 2 L of water. The precipitate was dried in a vacuum dryer, and a quinone diazide compound (D-1) represented by the following formula was obtained.

[0315]

[0316] <Synthesization Example 21 Synthesis of a Photosensitive Agent (Quinone Diazide Compound) (D-2)>

[0317] 21.2 g (0.05 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol (manufactured by Honshu Kagaku Kogyo Co., Ltd., hereinafter referred to as TrisP-PA) and 37.5 g (0.14 mol) of 4-naphthoquinone diazide sulfonic acid chloride (manufactured by Toyo Kosei Co., Ltd., NAC-5) were dissolved in 450 g of γ-butylolactone at room temperature under a dry nitrogen stream. To this, 12.7 g of triethylamine mixed with 50 g of γ-butylolactone was added dropwise so that the temperature in the system did not exceed 35°C. After adding, the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. Subsequently, the precipitated precipitate was collected by filtration and washed with 1 L of 1% hydrochloric acid solution. Afterwards, it was washed two more times with 2 L of water. The precipitate was dried in a vacuum dryer, and a quinone diazide compound (D-2) represented by the following formula was obtained.

[0318]

[0319] The structures and solvents of components (C-1), (C-2), (C-3), (C-4), and (C-5) used in the examples and comparative examples are shown below.

[0320]

[0321]

[0322] (C-1): YX-4000HK [Biphenyl-type cyclic ether type thermal crosslinking agent] (Manufactured by Mitsubishi Chemical Corporation)

[0323] (C-3): TMOM-BP [biphenyl-type alkoxymethyl type thermal crosslinking agent] (Manufactured by Honshu Kagaku Kogyo Co., Ltd.)

[0324] (C-4): HMOM-TPHAP [Triphenylmethane-type alkoxymethyl type thermal crosslinking agent] (Manufactured by Honshu Kagaku Kogyo Co., Ltd.)

[0325] Solvent: Gamma butylolactone (GBL)

[0326] [Examples 1–23, 25–43, Comparative Examples 1–16]

[0327] To the resins (A) (A-1) to (A-5) obtained in Synthesis Examples 4 to 8, (B) phenolic resins (B-1) to (B-11) obtained in Synthesis Examples 9 to 19, (C) thermal crosslinking agents (C-1) to (C-5), and photosensitive compounds (D-1) and (D-2) obtained in Synthesis Examples 20 to 21 were added in the mass parts shown in Tables 1 and 2, and GBL was used as a solvent to produce varnishes. These properties were measured by the evaluation method above. The constituent components and measurement results are shown in Tables 3 and 4.

[0328] [Table 1]

[0329]

[0330] [Table 2-1]

[0331]

[0332] [Table 2-2]

[0333]

[0334] [Table 3]

[0335]

[0336] [Table 4-1]

[0337]

[0338] [Table 4-2]

[0339] Explanation of the symbols

[0340] 1 : Display device 2 : Light-emitting element 3: Hardened film 4, 4c: Metal wiring 5: Opposing substrate 6: Electrode terminal 7: Light-emitting element driving substrate 8: Driving element 9 : Barrier Metal 10 : Solder vamp 11 : Bulkhead 12: Total thickness of the hardened film 13 : Substrate 14 : Inclined side 15: Angle of the inclined side 16: Hardened film

Claims

Claim 1 A resin composition comprising (A) one or more resins selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, (B) phenolic resin, (C) a thermal crosslinking agent, and (D) a photosensitive compound, wherein the (B) phenolic resin has a structural unit represented by general formula (4), and the structural unit represented by general formula (4) has a structural unit of general formula (5) and general formula (6), and when the total number of structural units represented by general formula (4) in the (B) phenolic resin is set to 100, the ratio of the number of structural units represented by general formula (5) and general formula (6) is general formula (5): general formula (6) = 60:40 to 90:

10. (In general formula (4), R 25 , R 27 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 , R 27 If multiple of these exist, they may be identical or different. R 26 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. j1 and j2 each independently represent integers from 0 to 3. (of general formula (5), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If multiple of these exist, they may be identical or different. j1 and j4 each independently represent integers from 0 to 3, and j3 represents an integer from 1 to 3. (of general formula (6), R 25 represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 25 If multiple instances of exist, they may be identical or different. R 26 It represents a hydrogen atom, or a monovalent organic group having 1 to 20 carbon atoms. R 28 R represents a monovalent organic group having 1 to 10 carbon atoms. 28 If there are multiple of these, they may be identical or different. j1 and j4 each represent an integer from 0 to 3 independently. However, the sum of j3 and j4 is j2. Claim 2 A resin composition according to claim 1, wherein the (C) thermal crosslinking agent may have a biphenyl structure having a substituent and / or a thermal crosslinking agent having a structural unit represented by the general formula (14). (In general formula (14), R 42 is a divalent organic group having an alkylene group or an alkylene ether group having 1 to 15 carbon atoms, R 43 and R 44 Each represents a hydrogen atom or a methyl group independently. Claim 3 In claim 2, (C) when the total amount of the thermal crosslinking agent is 100 mass%, the content ratio of the thermal crosslinking agent having a biphenyl structure that may have substituents and the thermal crosslinking agent having a structural unit represented by the general formula (14) is 15 mass% or more and 80 mass% or less. Claim 4 A resin composition having a general formula (12) or a general formula (13), wherein the thermocrosslinking agent having a biphenyl structure that may have a substituent in claim 2 or 3. (In general formula (12), R 29 and R 30 Each represents an independent hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms. R 29 , R 30 If multiple of these exist, they may be identical or different. R 31 , R 32 represents a thermal crosslinker. m1 and m2 each independently represent integers from 0 to 4, and m3 and m4 each independently represent integers from 1 to 3, satisfying 1 ≤ m1 + m3 ≤ 5 and 1 ≤ m2 + m4 ≤ 5. (In general formula (13), R 33 , R 34 , R 35 and R 36 Each represents a hydroxyl group or a monovalent organic group having 1 to 10 carbon atoms, independently. R 33 , R 34 , R 35 and R 36 If multiple of these exist, they may be identical or different. R 37 , R 38 , R 39 and R 40 represents a thermal crosslinker. R 41 n represents a monovalent organic group having 1 to 10 carbon atoms. n1, n4, n5, and n8 are each independently integers from 1 to 3, n2, n3, n6, and n7 are each independently integers from 0 to 4, n9 represents a repeating unit and is an integer from 1 to 10, and n10 represents an integer of 0 or 1. However, n1+n5≤5, n2+n6≤4, n3+n7≤4, and n4+n8≤4. Claim 5 A resin composition according to claim 2 or 3, wherein the (C) thermal crosslinking agent contains a thermal crosslinking agent having a biphenyl structure that may have the substituent, and the content of the thermal crosslinking agent having a biphenyl structure that may have the substituent is 30 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the (B) phenol resin. Claim 6 delete Claim 7 A resin sheet formed on a substrate using the resin composition described in claim 1. Claim 8 A resin composition described in any one of claims 1 to 3, or a cured film formed by curing a resin sheet described in claim 7. Claim 9 In claim 8, the hardened film has an opening pattern, and the angle of the inclined side in the cross-section of the opening pattern is 40° or more and 80° or less. Claim 10 A method for manufacturing a cured film comprising: a process of applying a resin composition described in any one of claims 1 to 3 to a substrate, or laminating a resin sheet described in claim 7 to a substrate, and then drying to form a resin film; an exposure process of exposing the dried resin film; a developing process of developing the exposed resin film; and a heat treatment process of heat treating the developed resin film. Claim 11 A semiconductor device having a hardened film as described in claim 8. Claim 12 An organic EL display device having at least a TFT substrate, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarization layer or the insulating layer comprises a cured film as described in claim 8. Claim 13 A display device having at least metal wiring, a cured film described in claim 8, and a plurality of light-emitting elements, wherein the light-emitting element has a pair of electrode terminals on one side thereof, the pair of electrode terminals are connected to a plurality of metal wirings extending into the cured film, and the plurality of metal wirings maintain electrical insulation by the cured film.

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