Photosensitive resin composition, photosensitive sheet, cured film thereof, method for producing the same, and electronic component

Abstract

The present invention provides a photosensitive resin composition having good pattern processability, and a cured film obtained by curing the composition at low temperature having high chemical resistance, high elasticity, high elongation and high adhesion to metal (especially copper). The present invention is a photosensitive resin composition, which contains: (A) a resin selected from any one or more of the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and polysiloxane; (B) a thermal base generator; and (C) a photosensitizer, wherein the (B) thermal base generator contains any one or more of a guanidine derivative or a biguanide derivative, and the (C) photosensitizer contains (c-1) a photoacid generator and / or (c-2) a photoradical polymerization initiator.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive sheet, and a cured film thereof and a method for producing the same, and an electronic component. More specifically, the present invention relates to a photosensitive resin composition, a photosensitive sheet, and a cured film thereof and a method for producing the same, and an electronic component, which are suitable for use as a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like. Background Art

[0002] As a representative material for the surface protection film of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and planarization films of TFT substrates, photosensitive polyimide resins that can be patterned and have excellent heat resistance and electrical insulation properties can be cited. In recent years, as a part of the high-integration countermeasures for semiconductors, semiconductor devices that form multi-layer metal rewiring have attracted attention. When forming such multi-layer metal rewiring, in order to reduce the warping of the substrate, measures are taken to reduce the curing temperature of the insulating film.

[0003] In addition, highly transparent and high-hardness photosensitive polysiloxanes are being studied as protective films for devices including display devices such as touch panels. In addition, there is an increasing demand for protecting substrates with low heat resistance, and low-temperature curing of polysiloxanes is desired.

[0004] In response to such a demand for low-temperature curing, the following methods have been studied, for example, as photosensitive polyimides: a method of curing at low temperature by combining a pre-imidized soluble polyimide with a crosslinking agent (Patent Document 1); a method of lowering the thermal curing temperature by imidizing during pattern processing using a photobase generator (Patent Document 2); etc. In addition, as photosensitive polysiloxanes, a method of combining siloxanes having highly reactive polymerizable groups with polymerization initiators has been studied (Patent Document 3).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2004 / 109403

[0008] Patent Document 2: Japanese Patent Application Publication No. 2010-133996

[0009] Patent Document 3: Japanese Patent Application Publication No. 2017-8147 Summary of the invention

[0010] Problems to be solved by the invention

[0011] In view of such social background, a technology for curing photosensitive insulating materials such as polyimide and polysiloxane at low temperature is sought. However, for example, in the technology of Patent Document 1, it is difficult to achieve both chemical resistance and crack resistance of the cured film, and in Patent Document 2, the sensitivity to exposure is low, so each has problems in terms of reliability and takt time. In addition, with regard to polysiloxane, the technology of Patent Document 3 has problems such as failure to obtain sufficient film hardness and poor storage stability.

[0012] The present invention solves the above-mentioned problems existing in the prior art and provides a photosensitive resin composition that can form a good pattern by a conventional photolithography process and has a cured film obtained by curing at a low temperature with excellent chemical resistance, adhesion and mechanical properties.

[0013] Means for solving problems

[0014] In order to solve the above-mentioned problems, the present invention relates to the following means.

[0015] That is, it relates to a photosensitive resin composition, which contains: (A) a resin, which is any one or more selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and polysiloxane; (B) a thermal base generator; and (C) a photosensitizer, wherein the (B) thermal base generator contains a guanidine derivative and / or a biguanide derivative, and the (C) photosensitizer contains (c-1) a photoacid generator and / or (c-2) a photoradical polymerization initiator.

[0016] The present invention also relates to a photosensitive sheet formed from the photosensitive resin composition.

[0017] The present invention also relates to a cured film obtained by curing the photosensitive resin composition or the photosensitive sheet.

[0018] In addition, the present invention relates to a method for producing a cured film, which includes the following steps: a step of coating the above-mentioned photosensitive resin composition on a substrate, or laminating the above-mentioned photosensitive sheet on a substrate, and drying to form a photosensitive resin film; a step of exposing the photosensitive resin film; a step of heat-treating the exposed photosensitive resin film; a step of developing the heat-treated photosensitive resin film; and a step of heat-treating the developed photosensitive resin film.

[0019] Furthermore, the present invention relates to an electronic component having the relief pattern of the cured film.

[0020] Effects of the Invention

[0021] The photosensitive resin composition and photosensitive sheet of the present invention have good pattern processability, and the cured film obtained by curing them at low temperature has excellent chemical resistance, adhesion and mechanical properties. In addition, the electronic component of the present invention has a pattern with excellent adhesion and chemical resistance and high reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] [ Figure 1 ] is a diagram showing an enlarged cross-section of a pad portion of a semiconductor device having a bump.

[0023] [ Figure 2 ] is a diagram showing a detailed method for manufacturing a semiconductor device having bumps. DETAILED DESCRIPTION

[0024] The present invention provides a photosensitive resin composition, which contains: (A) a resin, which is any one or more selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and polysiloxane; (B) a thermal base generator; and (C) a photosensitizer, wherein the (B) thermal base generator contains a guanidine derivative and / or a biguanide derivative, and the (C) photosensitizer contains (c-1) a photoacid generator and / or (c-2) a photoradical polymerization initiator. Each component is described below.

[0025] The photosensitive resin composition of the present invention contains (A) any one or more resins selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and polysiloxane (hereinafter, sometimes referred to as "(A) resin"). Among them, it is preferred to contain a polyimide precursor or a polysiloxane. As the polyimide precursor used in the (A) resin, for example, polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide can be cited. The polyamic acid with a tetracarboxylic acid residue and a diamine residue can be obtained by reacting an acid component with a diamine component.

[0026] Here, examples of the acid component include tetracarboxylic acid, tetracarboxylic dianhydride, and tetracarboxylic acid diester dichloride, etc. Examples of the diamine component include diamine, diisocyanate compounds, and trimethylsilylated diamine, etc.

[0027] The polyimide precursor as the (A) resin is preferably a resin containing a structural unit represented by the following general formula (6). In addition, it may contain two or more resins having the structural unit, or it may be a substance formed by copolymerizing two or more structural units. Among them, in order to reduce the thermal linear expansion coefficient while maintaining exposure sensitivity, a polyimide precursor having an acid residue of a biphenyl structure or an amine residue is preferred. That is, the above-mentioned (A) resin preferably contains a polyimide precursor having a biphenyl structure. In addition, in order to increase the elastic modulus, the above-mentioned (A) resin preferably contains a polyimide precursor having a residue of an amino compound having a valence of 3 or more.

[0028] [Chemical formula 1]

[0029]

[0030] In the general formula (6), X represents a tetravalent to tetravalent organic group having 2 or more carbon atoms. Y each independently represents a divalent to tetravalent organic group having 2 or more carbon atoms. a , R b Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. p and q each independently represent an integer of 0 to 4, r represents an integer of 2 to 8, and s represents an integer of 0 to 8. When the value of p, q, r, and s is 0, the functional groups in the brackets represent hydrogen atoms. Here, in this specification, when "to" is expressed, it means that the number includes the upper and lower limits unless otherwise specified.

[0031] In general formula (6), X is derived from a tetra-, hexa-, octa- or decacarboxylic acid residue or a residue of a derivative thereof (hereinafter collectively referred to as "acid residue"). In addition, by using an acid component corresponding to the acid residue during polymerization, the structural unit can contain the acid residue. Examples of the carboxylic acid compound in which X is an acid residue include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-

[0063] The invention also includes bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, aromatic tetracarboxylic acids such as 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-perylenetetracarboxylic acid, or aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1.]heptanetetracarboxylic acid, bicyclo[3.3.1.]tetracarboxylic acid, bicyclo[3.1.1.]hept-2-enetetracarboxylic acid, bicyclo[2.2.2.]octanetetracarboxylic acid or adamantanetetracarboxylic acid. Among these, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, and 2,2',3,3'-biphenyltetracarboxylic acid are preferred in order to achieve both high exposure sensitivity and low thermal linear expansion coefficient.

[0032] [Chemical formula 2]

[0033]

[0034] [Chemical formula 3]

[0035]

[0036] In the above formula, multiple R c It represents any of the following structures.

[0037] [Chemical formula 4]

[0038]

[0039] These acids can be used directly, or in the form of anhydrides, acid chlorides or active esters. Examples of active ester groups include the following structures, but are not limited thereto.

[0040] [Chemical formula 5]

[0041]

[0042] In the formula, A and D include, but are not limited to, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, a nitro group and the like.

[0043] Preferred structures of the acid residue of X include, for example, the following structures or structures in which 1 to 4 hydrogen atoms are substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group, a fluorine atom or a chlorine atom.

[0044] [Chemical formula 6]

[0045]

[0046] [Chemical formula 7]

[0047]

[0048] Wherein, J represents a direct bond, -COO-, -CONH-, -CH2-, -C2H4-, -O-, -C3H6-, -SO2-, -S-, -Si(CH3)2-, -O-Si(CH3)2-O-, -C6H4-, -C6H4-O-C6H4-, -C6H4-C3H6-C6H4- or -C6H4-C3F6-C6H4-.

[0049] In addition, by using a tetracarboxylic acid containing a silicon atom such as dimethylsilanediphthalic acid or 1,3-bis(phthalate)tetramethyldisiloxane, it is possible to improve adhesion to a substrate and resistance to oxygen plasma and UV ozone treatment used in cleaning, etc. These tetracarboxylic acids containing a silicon atom are preferably used in an amount of 1 to 30 mol% of the total acid components.

[0050] In the general formula (6), Y represents a di-, tri-, tetra-, penta-, hexa-, hepta-, or octaamine residue or an isocyanate residue (hereinafter collectively referred to as "amine residue"). In addition, by using an amine compound or isocyanate compound having a structure of the amine residue during polymerization, the amine residue can be contained in the structural unit.

[0051] Examples of the amine component in which Y is an amine residue include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 2,7-diaminofluorene, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, and 4-aminobenzoic acid-4 -aminophenyl ester, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(4-anilino)tetramethyldisiloxane, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis [4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2-(4-aminophenyl)-5-aminobenzooxazole, 2-(3-aminophenyl)-5-aminobenzooxazole, 2-(4-aminophenyl)-6-aminobenzooxazole, 2-(3-aminophenyl)-6-aminobenzooxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene Aromatic diamines such as bis(3-aminophenyl)-5-benzoxazole], bis(4-aminophenyl)-5-benzoxazole], bis(3-aminophenyl)-6-benzoxazole], bis(4-aminophenyl)-6-benzoxazole], bis(3-aminophenyl)-6-benzoxazole], bis(3-aminophenyl)-4-hydroxyphenyl)-6-benzoxazole, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 4,4'-Diamino-6,6'-bis(trifluoromethyl)-[1,1'-biphenyl]-3,3'-diol, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4- 2,2'-Bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl] 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, Bisaminophenols such as N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl and N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, compounds in which a part of the hydrogen atoms of the aromatic rings are substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc., and diamines having the following structures, but not limited thereto.

[0052] [Chemical formula 8]

[0053]

[0054] [Chemical formula 9]

[0055]

[0056] Among these, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biaminobiphenyl, and 2,2'-dimethyl-4,4'-biaminobiphenyl are preferred from the viewpoint of heat resistance. 4,4'-biaminobiphenyl, 2,2'-dimethyl-4,4'-biaminobiphenyl, 2,2'-diethyl-4,4'-biaminobiphenyl, 3,3'-dimethyl-4,4'-biaminobiphenyl, 3,3'-diethyl-4,4'-biaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-biaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-biaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4 '-diaminobiphenyl, bis(3-amino-4-hydroxy)biphenyl, 4,4'-diamino-6,6'-bis(trifluoromethyl)-[1,1'-biphenyl]-3,3'-diol, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl. From the viewpoint of elongation, 4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and 4,4'-diaminobenzophenone are preferred. The other copolymerized diamine may be used as it is, or as a compound in which the amine moiety is isocyanated or trimethylsilylated. In addition, two or more diamine components may be used in combination.

[0057] In addition to the above-mentioned aromatic diamines, aliphatic diamines or diamines having a siloxane structure may be mentioned. Examples of the aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propylenediamine, 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, 4,4-bis(aminomethyl)cyclohexane, and 1,2-bis(aminomethyl)cyclohexane. '-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, (the above are trade names, manufactured by HUNTSMAN (KK)), etc. Among the above, it is preferred that an alkylene oxide structure is contained from the viewpoint of further increasing flexibility and achieving high elongation. In addition, due to the presence of the ether group in the above-mentioned alkylene oxide structure, a complex can be formed with the metal, a hydrogen bond can be formed, and high adhesion with the metal can be obtained. In addition, it can also contain bonds such as -S-, -SO-, -SO2-, -NH-, -NCH3-, -N(CH2CH3)-, -N(CH2CH2CH3)-, -N(CH(CH3)2)-, -COO-, -CONH-, -OCONH-, and -NHCONH-.

[0058] As the diamine having a siloxane structure, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are preferred because they can improve adhesion to the substrate.

[0059] In addition to the above-mentioned diamine components, trivalent or higher amine compounds can be mentioned. When the (A) resin has a residue of a trivalent or higher amine compound, a cured film obtained by curing exhibits a high elastic modulus. Specific examples of the trivalent or higher amine compound include tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenoxy)benzene, 1,3,5-tris(4-aminophenyl)benzene, 2,4,4'-triaminodiphenyl ether, 3,4,4'-triaminodiphenyl ether, 2,4,4'-triaminodiphenyl sulfone, 3,4,4'-triaminodiphenyl sulfone, 2,4,4'-triaminodiphenyl sulfide, 3,4,4'-triaminodiphenyl sulfide, 2,4,4'-triaminobenzophenone, 3,4,4'-triaminobenzophenone, tris(4-aminophenyl)methane, 1,1,1-tris(4-aminophenyl)ethane, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris(4-aminophenoxy)-1,3,5-triazine, N 2 ,N 4 ,N 6 - tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine, tris(hexylamino)isocyanurate, and triamine, tetramine or pentamine having the following structure.

[0060] [Chemical formula 10]

[0061]

[0062] In the general formula (6), R a and R b represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. When the obtained photosensitive resin composition is a positive type, R a Preferably, they are a hydrogen atom, a methyl group or an ethyl group. a and R b From the viewpoint of alkali solubility, a hydrogen atom is preferred. When the obtained photosensitive resin composition is a negative type, an organic group having an ethylenically unsaturated bond improves the sensitivity to exposure and is therefore preferred.

[0063] As for the method for introducing an organic group having an ethylenically unsaturated bond, for example, it can be obtained by reacting tetracarboxylic dianhydride with alcohols having an ethylenically unsaturated bond to generate a tetracarboxylic acid diester, and then subjecting it to an amide polycondensation reaction with an amine compound having a Y structure. In addition, when hexacarboxylic acid trianhydride, octacarboxylic acid tetraanhydride, or decacarboxylic acid pentaanhydride is used, it can also be obtained by the same operation.

[0064] As a method for generating the above-mentioned tetracarboxylic acid diester, the above-mentioned acid dianhydride and alcohol can also be directly reacted in a solvent, but from the viewpoint of reactivity, a reaction activator is preferably used. As a reaction activator, tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene can be mentioned. As an added amount of the reaction activator, relative to the acid anhydride group of the reaction, it is preferably 10mol% to 300mol%, and more preferably 50mol% to 150mol%. In addition, in order to prevent the ethylenically unsaturated bond site from crosslinking during the reaction, a small amount of polymerization inhibitor can be used. Thus, in the reaction of alcohols with ethylenically unsaturated bonds with tetracarboxylic dianhydride having low reactivity, heating in a range of 120°C or less can promote the reaction. As a polymerization inhibitor, phenol compounds such as hydroquinone, 4-methoxyphenol, tert-butylcatechol, and bis-tert-butylhydroxytoluene can be mentioned. The amount of the polymerization inhibitor added is preferably 0.1 mol% to 5 mol% of the phenolic hydroxyl group of the polymerization inhibitor relative to the ethylenically unsaturated bonds of the alcohol.

[0065] Various methods can be used for the amide polycondensation reaction, including: a method of reacting a tetracarboxylic acid diester with a diamine after chlorination; a method of using a carbodiimide-based dehydration condensation agent; and a method of reacting a tetracarboxylic acid diester with a diamine after active esterification.

[0066] Examples of the alcohols having the ethylenically unsaturated bond include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2-propanol, 2-(meth)acrylamideethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-tert-butoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexylalkoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate. Alcohols having one ethylenically unsaturated bond and one hydroxyl group, glycerol-1,3-di(meth)acrylate, glycerol-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol-1-allyloxy-3-methacrylate, glycerol-1-allyloxy-2-methacrylate, bis(2-methacrylate)2-ethyl-2-(hydroxymethyl)propane-1,3-diester, methacrylate-2-((acryloyloxy)-2-(hydroxymethyl)butyl, etc. having two or more ethylenically unsaturated bonds and one hydroxyl group. Here, "(meth)acrylate" means methacrylate or acrylate. The same applies to similar expressions.

[0067] When the acid anhydride and the alcohol having an ethylenically unsaturated bond are reacted, other alcohols may be used simultaneously. Other alcohols may be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in an organic solvent. Specifically, examples include aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and isopentanol; or monohydric alcohols derived from alkylene oxides such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and tripropylene glycol monobutyl ether.

[0068] In the general formula (6), R aOther methods for preparing an organic group having 1 to 20 carbon atoms include, for example, a method of obtaining a polyamic acid from an acid dianhydride and a diamine and then esterifying the polyamic acid using a known method. Examples of the esterification reaction include: a method using trifluoroacetic acid and a compound having a hydroxyl group; a method of reacting dimethylformamide dialkyl acetal; and the like.

[0069] In addition, in order to improve the storage stability of the photosensitive resin composition of the present invention and to make it present various functions, the main chain end of the resin (A) can also be blocked with an end-blocking agent. As the end-blocking agent, monoamines, acid anhydrides, monocarboxylic acids, monoacyl chloride compounds, monoactive ester compounds, etc. can be cited. In addition, in the later stage of the reaction of the above-mentioned amide polycondensation, monohydric alcohols can also be used as end-blocking agents. In addition, by blocking the ends of the resin with an end-blocking agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an acetylene group or an allyl group, the dissolution rate of the resin in an alkaline solution, the exposure sensitivity, the mechanical properties of the obtained cured film, etc. can be easily adjusted to a preferred range.

[0070] From the viewpoint of solubility in a developer and mechanical properties of the obtained cured film, the introduction ratio of the end-capping agent is preferably 0.1 mol% to 60 mol%, particularly preferably 5 mol% to 50 mol%. A plurality of end-capping agents may be reacted to introduce a plurality of different terminal groups.

[0071] Preferred monoamines used as the end-capping agent include M-600, M-1000, M-2005, and M-2070 (these are trade names, manufactured by Huntsman Co., Ltd.), aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, and 1-carboxy-7-aminonaphthalene. , 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of them may be used.

[0072] As the acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, or 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxy Monocarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, monocarboxylic acid compounds obtained by chlorinating only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, active ester compounds obtained by reacting monocarboxylic acid compounds with N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboxyimide, etc. Two or more of these may be used.

[0073] Examples of the monohydric alcohol used as the terminal blocking agent include those exemplified as the alcohols that react with the above-mentioned acid anhydride.

[0074] In addition, the end-capping agent introduced into the (A) resin used in the present invention can be easily detected using the following method. For example, the resin introduced with the end-capping agent is dissolved in an acidic solution, decomposed into amine components and anhydride components as structural units, and subjected to gas chromatography (GC) and NMR measurement, thereby the end-capping agent used in the present invention can be easily detected. In addition, by simultaneously performing GC measurement on each component and an external standard substance whose peaks do not overlap, and comparing the integral value of each peak in the chromatogram with the external standard substance, the molar ratio of each monomer containing the end-capping agent can be estimated. In addition, by directly using thermal decomposition gas chromatography (PGC), infrared spectroscopy, 1 H-NMR spectroscopy, 13 C-NMR spectroscopy and two-dimensional NMR spectroscopy can also be used to easily detect the resin component into which the end-capping agent has been introduced. 1 The molar ratio of each monomer can be analyzed by the integrated value of the H-NMR spectrum or the two-dimensional NMR.

[0075] The polyimide as the resin (A) can be obtained by partially dehydrating and ring-closing the polyimide precursor by heat treatment or chemical treatment based on acid, alkali, etc. More specifically, a solvent that azeotropes with water, such as m-xylene, can be added for heat treatment, or a weakly acidic carboxylic acid compound can be added for heat treatment at a low temperature below 100°C. As the ring-closing catalyst used in the above-mentioned chemical treatment, for example, a dehydration condensation agent such as carboxylic anhydride or dicyclohexylcarbodiimide or a base such as triethylamine can be cited. In addition, it can be obtained by polymerizing an amine compound or a carboxylic acid compound containing an imide group as a residue as a monomer.

[0076] The polybenzoxazole precursor of the resin (A) includes, for example, copolymers with polyhydroxyamide, polyaminoamide, polyamide or polyamideimide, preferably polyhydroxyamide. The polyhydroxyamide having a dicarboxylic acid residue and a bisaminophenol residue can be obtained by reacting bisaminophenol with a dicarboxylic acid or a corresponding dicarboxylic acid chloride or a dicarboxylic acid active ester.

[0077] Examples of dicarboxylic acids that are monomers of the polyhydroxyamide include cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, and nonanedicarboxylic acid. Aliphatic dicarboxylic acids such as 1,2-dihydro-1,3 ... Examples of the bisaminophenol include the bisaminophenols exemplified in the above-mentioned amine component in which Y is an amine residue.

[0078] The polybenzoxazole as the resin (A) is preferably a copolymer with other resins from the viewpoint of solubility. For example, a polyimide precursor-polybenzoxazole copolymer can be obtained by polymerizing a polyimide precursor using an amine compound (having a benzoxazole moiety as a residue) or a carboxylic acid derivative as a monomer.

[0079] In addition, (A) resin can be a copolymer. Among them, preferably polyimide precursor-polyimide copolymer, polyimide precursor-polybenzoxazole precursor copolymer. Polyimide precursor-polyimide copolymer is obtained in the following manner: during the polymerization of polyimide precursor, a part of it is thermally imidized or chemically imidized. Polyimide precursor-polybenzoxazole precursor copolymer is obtained in the following manner: during and / or before and after the reaction period of obtaining the above-mentioned polyimide precursor, the above-mentioned polyhydroxyamide is polymerized. In addition, by using an amine compound (which has a hydroxyamide site as a residue) or a carboxylic acid compound as the polymerization of a monomeric polyimide precursor in advance, it can also be obtained.

[0080] As the epoxy resin of the resin (A), there can be mentioned resins obtained by glycidylating phenolic compounds. As phenolic compounds, there can be mentioned low molecular weight compounds such as bisphenol A, bisphenol F, bisphenol E, bisphenol AF, bisphenol S, bisphenol fluorene, biphenol, trisphenol methane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and phenolic resins obtained by polycondensation of phenolic low molecular weight compounds and aldehyde compounds represented by Novolac resin, but are not limited to these. Among them, resins obtained by glycidylating bisphenol A modified phenolic resins and Novolac resins have excellent reactivity and are preferred.

[0081] The polysiloxane as the resin (A) is a hydrolysis-dehydration condensate of an organosilane, and in the present invention, preferably has a hydrophilic group. By having a hydrophilic group in the polysiloxane, the developability can be further improved, and the developer residue can be further suppressed. In addition, it is more preferable to have a styryl group. By having a styryl group in the polysiloxane, the hardness and chemical resistance can be further improved.

[0082] As the hydrophilic group, for example, a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, a hydroxyimide group, etc. can be mentioned. Two or more of these can be present. Among these, from the viewpoint of further suppressing the developing residue and further improving the storage stability, a carboxyl group and a carboxylic acid anhydride group are preferred, and a carboxylic acid anhydride group is more preferred.

[0083] The polysiloxane having a hydrophilic group and a styryl group can be obtained, for example, by hydrolyzing and dehydrating a plurality of organosilane compounds including an organosilane compound having a hydrophilic group and an organosilane compound having a styryl group. An organosilane compound other than an organosilane compound having a hydrophilic group and a free radical polymerizable group may be hydrolyzed and dehydrated together with the organosilane compound.

[0084] As the organosilane compound having a hydrophilic group, an organosilane compound having a carboxylic acid group and / or a carboxylic acid anhydride group is preferred, and an organosilane compound having a carboxylic acid anhydride group is more preferred. For example, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, etc. can be cited.

[0085] The polysiloxane having a styryl group can be obtained, for example, by the following method: a plurality of organosilane compounds including an organosilane compound having a styryl group are hydrolyzed and dehydrated and condensed. As the organosilane compound having a styryl group, styryltrimethoxysilane and styryltriethoxysilane are preferred, and styryltrimethoxysilane is more preferred. In addition, as organosilane compounds other than organosilane compounds having a hydrophilic group and a styryl group, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- -(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxysilane, α-glycidyltrimethoxysilane, α-glycidylethyltriethoxysilane, β-glycidyltrimethoxysilane, β-glycidylpropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyltriethoxysilane, Oxypropyl triethoxysilane, γ-glycidoxypropyl tripropoxysilane, γ-glycidoxypropyl triisopropoxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyl tri(methoxyethoxy)silane, α-glycidoxybutyl trimethoxysilane, α-glycidoxybutyl triethoxysilane, β-glycidoxybutyl trimethoxysilane, β-glycidoxybutyl triethoxysilane, γ-glycidoxybutyl trimethoxysilane, γ-glycidoxybutyl triethoxysilane, σ-glycidoxybutyl trimethoxysilane, σ-glycidoxybutyl triethoxysilane, (3,4-cyclopropane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 2-(3,4-ep4-Epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropyl Methyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylbis(methoxyethoxy)silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, etc. Two or more of them may be used. ,

[0086] The polysiloxane can be obtained by hydrolyzing the above-mentioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or in the absence of a solvent.

[0087] The various conditions for hydrolysis can be set according to the physical properties suitable for the intended use, taking into account the reaction scale, the size and shape of the reaction container, etc. Examples of the various conditions include acid concentration, reaction temperature, reaction time, and the like.

[0088] In the hydrolysis reaction, acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid and its anhydride, ion exchange resin, etc. can be used. Among these, acidic aqueous solutions containing formic acid, acetic acid and / or phosphoric acid are preferred.

[0089] When an acid catalyst is used in the hydrolysis reaction, from the viewpoint of making the hydrolysis proceed more rapidly, the amount of the acid catalyst added is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of all alkoxysilane compounds used in the hydrolysis reaction. On the other hand, from the viewpoint of appropriately regulating the progress of the hydrolysis reaction, the amount of the acid catalyst added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of all alkoxysilane compounds. Here, the amount of all alkoxysilane compounds refers to the amount including all of the alkoxysilane compounds, their hydrolyzates, and their condensates. The hydrolysis reaction can be carried out in a solvent.

[0090] The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive siloxane resin composition. Among these, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-tert-butyl ether, γ-butyrolactone, etc. are preferably used from the viewpoints of transmittance and crack resistance of the cured film.

[0091] When a solvent is generated by the hydrolysis reaction, the hydrolysis may be performed without a solvent. It is also preferred to further add a solvent after the hydrolysis reaction is completed to adjust the photosensitive resin composition to an appropriate concentration. In addition, the entire amount or a portion of the generated alcohol etc. may be distilled off and removed by heating and / or reduced pressure after the hydrolysis, and then a suitable solvent may be added.

[0092] When a solvent is used in the hydrolysis reaction, from the viewpoint of suppressing the formation of gel, the amount of the solvent added is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, relative to 100 parts by mass of the total alkoxysilane compound. On the other hand, from the viewpoint of causing the hydrolysis to proceed more rapidly, the amount of the solvent added is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, relative to 100 parts by mass of the total alkoxysilane compound.

[0093] In addition, as water used for the hydrolysis reaction, ion-exchanged water is preferred. The amount of water can be set arbitrarily, but is preferably 1.0 to 4.0 mol based on 1 mol of all alkoxysilane compounds.

[0094] As a method for the dehydration condensation reaction, for example, a method of directly heating a silanol compound solution obtained by the hydrolysis reaction of an organic silane compound can be cited. The heating temperature is preferably above 50° C. and below the boiling point of the solvent, and the heating time is preferably 1 to 100 hours. In addition, in order to increase the degree of polymerization of the polysiloxane, reheating or the addition of an alkali catalyst can be performed. In addition, according to the purpose, an appropriate amount of generated alcohol can be distilled out and removed by heating and / or reduced pressure after hydrolysis, and then a suitable solvent can be added.

[0095] From the viewpoint of storage stability of polysiloxane, the polysiloxane solution after hydrolysis and dehydration condensation preferably does not contain the above-mentioned catalyst, and the catalyst can be removed as needed. As a catalyst removal method, from the viewpoint of simplicity of operation and removability, water washing, treatment based on ion exchange resin, etc. are preferably performed. Water washing refers to a method in which the polysiloxane solution is diluted with an appropriate hydrophobic solvent, washed with water several times, and the obtained organic layer is concentrated using an evaporator or the like. Treatment based on ion exchange resin refers to a method in which the polysiloxane solution is contacted with an appropriate ion exchange resin.

[0096] The weight average molecular weight of the (A) resin in the present invention is preferably 5,000 to 100,000. By making the weight average molecular weight (based on GPC (gel permeation chromatography) and calculated in terms of polystyrene) 5,000 or more, mechanical properties such as elongation after curing, breaking point strength, and elastic modulus can be improved. On the other hand, by making the weight average molecular weight 100,000 or less, the developability can be improved. In order to obtain mechanical properties, it is more preferably 20,000 or more. In addition, when the (A) resin contains two or more resins, the weight average molecular weight of at least one of them can be within the above range.

[0097] In addition, the (A) resin used in the present invention is preferably polymerized using a solvent. The polymerization solvent is not particularly limited in type as long as it can dissolve the acid component, amine component, alcohol, and catalyst as the raw material monomer. For example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyramide, methoxy-N,N-dimethylpropionamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, cyclic esters such as α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclopentane, dimethyl sulfoxide, etc. can be cited.

[0098] The photosensitive resin composition of the present invention contains (B) a thermal base generator. The above-mentioned (B) thermal base generator is a guanidine derivative and / or a biguanide derivative (hereinafter, sometimes referred to as "(B) component"). By containing the (B) component, the ring-closing reaction of the (A) resin is promoted in the thermal curing process, and polyimide can be obtained even in a low temperature range below 250°C. As a result, the mechanical properties, especially the elongation and breaking point strength of the cured film formed by curing the photosensitive resin composition of the present invention can be improved. In addition, the adhesion between the cured film and the metal substrate can be improved. The above-mentioned (B) thermal base generator preferably contains a guanidine derivative and / or a biguanide derivative having a quaternary boron anion. The (B) component can be classified into nonionic and ionic, and ionic base generators are highly active and therefore preferred. In addition, the base generated by the biguanide derivative has a high basicity and is therefore preferred. Among them, the compound represented by the general formula (1) is particularly preferred.

[0099] [Chemical formula 11]

[0100]

[0101] In the general formula (1), R 1 ~R 7 Each independently represents a hydrogen atom or a substituted or unsubstituted group, wherein the group is an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or an arylalkyl group having 7 to 50 carbon atoms, and Z - represents a carboxylate or borate anion.

[0102] In the general formula (1), R 1 ~R 7 The alkyl group having 1 to 50 carbon atoms represented by the formula (A) may be any of a linear, branched or cyclic group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl, cycloheptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, neooctyl, 2-ethylhexyl, cyclooctyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl, cyclononyl, n-decyl, isodecyl, sec-decyl, tert-decyl, neodecyl, cyclodecyl, n-undecyl, cycloundecyl, n-dodecyl, cyclododecyl, norbornyl, bornyl, Among these, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl and 2-ethylhexyl are preferred from the viewpoint of stability and solubility of the compound.

[0103] The aryl group having 6 to 50 carbon atoms may be either a monocyclic group or a condensed polycyclic group, and specific examples thereof include phenyl, naphthyl, anthracenyl, and phenanthryl.

[0104] The arylalkyl group having 7 to 50 carbon atoms may be any of a monocyclic group or a condensed polycyclic group. Specific examples thereof include benzyl, phenethyl, methylbenzyl, phenylpropyl, 1-methylphenylethyl, phenylbutyl, 2-methylphenylpropyl, tetrahydronaphthyl, naphthylmethyl, naphthylethyl, indenyl, fluorenyl, anthracenylmethyl, and phenanthrenylmethyl.

[0105] In the general formula (1), R 1 ~R 7 When the organic group represented is other than a hydrogen atom, it may be substituted. As a substituent of the alkyl group having 1 to 50 carbon atoms, there can be mentioned an amino group, a nitro group, an epoxy group, an alkoxycarbonyl group, a vinyl group, a (meth)acryloyl group, an ethynyl group, a coumarinylcarbonyl group, an anthraquinone group, a xanthone group, and a thioxanthone group. As specific examples of epoxy groups, there can be mentioned a glycidyl group and a 2,3-cyclohexyloxirane group. As specific examples of alkoxycarbonyl groups, there can be mentioned a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, a n-isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a cyclobutoxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a neopentyloxycarbonyl group, a 2-methylbutoxycarbonyl group, a 1,2-dimethylpropoxycarbonyl group, a 1-ethylpropoxycarbonyl group, a cyclopentyloxycarbonyl group, and the like. Specific examples of the amino group include, in addition to unsubstituted primary amino groups, secondary or tertiary amino groups substituted with an alkyl group having 1 to 4 carbon atoms, such as methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, diisopropylamino, n-butylamino, di-n-butylamino, isobutylamino, diisobutylamino, sec-butylamino, di-sec-butylamino, tert-butylamino, di-tert-butylamino, cyclobutylamino, and dicyclobutylamino.

[0106] As a substituent of the aryl group having 6 to 50 carbon atoms or the arylalkyl group having 7 to 50 carbon atoms, an alkyl group, an alkoxy group, a coumarinylcarbonyl group, an anthraquinone group, a xanthone group, a thioxanthone group, a halogen atom and a nitro group can be mentioned. As an alkyl group, any of linear, branched or cyclic can be mentioned, and as a specific example, the groups exemplified in the alkyl group having 1 to 50 carbon atoms can be mentioned. As an alkoxy group, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a neopentyloxy group, a 2-methylbutoxy group, a 1,2-dimethylpropoxy group, a 1-ethylpropoxy group, a cyclopentyloxy group, a n-hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, a neohexyloxy group, a 2-methylpentyloxy group, a 1,2-dimethylbutoxy group, a 2,3-dimethylbutoxy group, a 1-ethylbutoxy group, a cyclohexyloxy group and the like can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0107] In the general formula (1), specific structures of the biguanide cation include the following structures.

[0108] [Chemical formula 12]

[0109]

[0110] [Chemical formula 13]

[0111]

[0112] In the general formula (1), Z - represents a carboxylate or borate anion. - Examples of the carboxylate radical include carboxylates derived from aliphatic carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid, and aromatic carboxylic acid compounds such as benzoic acid, 4-benzoylbenzoic acid, salicylic acid, cinnamic acid, and 4-biphenylcarboxylic acid. In addition, examples include carboxylates represented by the general formula (2) and the general formula (3), which are preferred from the viewpoint of the storage stability of the photosensitive resin composition of the present invention.

[0113] [Chemical formula 14]

[0114]

[0115] In the general formula (2), R 8 ~R 16 Each independently represents a hydrogen atom, a halogen atom, a nitro group, or a substituted or unsubstituted group which is an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group having 7 to 50 carbon atoms, or an alkoxy group having 1 to 50 carbon atoms.

[0116] [Chemical formula 15]

[0117]

[0118] In the general formula (3), R 17 ~R 25 Each independently represents a hydrogen atom, a halogen atom, a nitro group, or a substituted or unsubstituted group which is an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group having 7 to 50 carbon atoms, or an alkoxy group having 1 to 50 carbon atoms; and Y represents an oxygen atom or a sulfur atom.

[0119] As R in the general formula (2) 8 ~R 16 and, R in the general formula (3) 17 ~R 25 The alkyl group having 1 to 50 carbon atoms represented by the formula (1) may be linear, branched or cyclic. Specific examples thereof include: 1 ~R 7 The same applies to the substituents when substituted. For the aryl group having 6 to 50 carbon atoms and the arylalkyl group having 7 to 15 carbon atoms, R in the general formula (1) can be exemplified. 1 ~R 7 The groups exemplified in the description of are the same as the substituents when substituted. Examples of the alkoxy group having 1 to 50 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, neopentoxy, 2-methylbutoxy, 1,2-dimethylpropoxy, 1-ethylpropoxy, cyclopentoxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, neohexyloxy, 2-methylpentoxy, 1,2-dimethylbutoxy, 2,3-dimethylbutoxy, 1-ethylbutoxy, and cyclohexyloxy. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0120] As specific structures of the carboxylate group represented by the general formula (2) or (3), the following structures can be mentioned.

[0121] [Chemical formula 16]

[0122]

[0123] In the general formula (1), as the Z -The borate may include, in addition to borates containing a hydrogen atom or a halogen atom such as tetrahydroborate, tetrafluoroborate, tetrachloroborate, tetrabromoborate, etc., borates represented by the following general formula (4) are preferred from the viewpoint of storage stability.

[0124] [Chemical formula 17]

[0125]

[0126] In the general formula (4), R 26 ~R 29 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted group selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkynyl group having 2 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group having 7 to 50 carbon atoms, an arylalkynyl group having 7 to 50 carbon atoms, a furyl group, a thienyl group, or a pyrrolyl group.

[0127] As R in the general formula (4) 26 ~R 29 The alkyl group having 1 to 50 carbon atoms, the alkoxy group having 1 to 50 carbon atoms, the aryl group having 6 to 50 carbon atoms, and the arylalkyl group having 7 to 50 carbon atoms represented by the general formula (1) include: 1 ~R 7 The groups exemplified in the description of are the same as the substituents when substituted. Examples of the alkenyl group having 2 to 50 carbon atoms include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, isobutenyl, methacryloyl, isoprenyl, isopentenyl, cyclopentenyl, n-hexenyl, cyclohexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, etc.

[0128] Examples of the alkynyl group having 2 to 50 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, and 3-butynyl.

[0129] Examples of the arylalkynyl group having 7 to 50 carbon atoms include phenylethynyl, 3-phenylpropynyl, 4-phenylbutynyl, 5-phenylpentynyl and 6-phenylhexynyl. The pyrrolyl group may be an N-substituted group, for example, N-methylpyrrolyl, N-ethylpyrrolyl, N-n-propylpyrrolyl, N-isopropylpyrrolyl, N-n-butylpyrrolyl, N-isobutylpyrrolyl, N-sec-butylpyrrolyl, N-tert-butylpyrrolyl, N-cyclobutylpyrrolyl, N-n-pentylpyrrolyl, N-isopentylpyrrolyl, N-sec-pentylpyrrolyl, N-tert-pentylpyrrolyl, N-neopentylpyrrolyl, N-cyclopentylpyrrolyl, N-n-hexylpyrrolyl, N-isohexylpyrrolyl, N-sec-hexylpyrrolyl, N-tert-hexylpyrrolyl, N-neohexylpyrrolyl, N-2-methylpentylpyrrolyl, N-cyclohexylpyrrolyl and the like.

[0130] In general formula (4), R 26 ~R 29 The organic group represented by may be substituted except for hydrogen atoms and halogen atoms. Specific examples of the substituents of the alkyl group having 1 to 50 carbon atoms, the aryl group having 6 to 50 carbon atoms, and the arylalkyl group having 7 to 50 carbon atoms are respectively the same as those in R in the general formula (1). 1 ~R 7 The above-mentioned groups are the same as those in the organic groups shown. Among them, a halogen atom or a nitro group is preferred, and a fluorine group is more preferred. As substituents for the alkenyl group having 2 to 50 carbon atoms, the alkynyl group having 2 to 50 carbon atoms, the arylalkynyl group having 7 to 50 carbon atoms, the furyl group, the thienyl group, and the pyrrolyl group, the same substituents as those exemplified as substituents for the aryl group having 6 to 50 carbon atoms can be cited.

[0131] Among the borate anions represented by the general formula (4), the anions represented by the following general formula (5) are preferred because they have better storage stability.

[0132] [Chemical formula 18]

[0133]

[0134] In the general formula (5), R 30 represents a substituted or unsubstituted group, wherein the group is an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkynyl group having 2 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, an arylalkyl group having 7 to 50 carbon atoms, an arylalkynyl group having 7 to 15 carbon atoms, a furyl group, a thienyl group or a pyrrolyl group, and R 31 ~R 33 It represents an aryl group having 6 to 50 carbon atoms.

[0135] In addition, in the general formula (5), R 31 ~R 33The aryl group is preferably substituted with an electron withdrawing group. Examples of the electron withdrawing group include fluorine atoms, chlorine atoms, bromine atoms, nitro groups, etc., of which fluorine atoms are preferred. In addition, when the alkyl group having 1 to 50 carbon atoms and the aryl group having 6 to 50 carbon atoms each contain one or more, the solubility in an organic solvent is high, which is preferred.

[0136] Specific examples of the borate anion represented by the general formula (4) include the following anions.

[0137] [Chemical formula 19]

[0138]

[0139] [Chemical formula 20]

[0140]

[0141] Specific examples of the component (B) include any combination of the specific examples of the biguanide cations described above and the specific examples of the carboxylate anions or borate anions. Other specific examples include 1,5,7-triazabicyclo[4.4.0]dec-5-ene acetate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene benzoate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene 2-(9-oxoxanthene-2-yl)propanoic acid-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-(3-benzoylphenyl)guanidine propionate, guanidine acetate, guanidine phosphate, guanidine benzoate, L-arginine, L-arginine acetate, L-arginine phosphate, L-arginine benzoate, and the like.

[0142] The content of component (B) is not particularly limited, but is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the polyimide precursor (A). By making it within this range, it is possible to appropriately maintain pattern processability, solubility, and storage stability while promoting the ring-closure reaction of the polyimide precursor (A). It is preferably 0.3 to 7 parts by mass, and more preferably 0.5 to 5 parts by mass.

[0143] The photosensitive resin composition of the present invention contains (C) a photosensitizer. The above-mentioned (C) photosensitizer contains (c-1) a photoacid generator and / or (c-2) a photoradical polymerization initiator. By containing the (C) photosensitizer, pattern processing can be performed through exposure and development steps.

[0144] The photoacid generator (c-1) is not particularly limited, but preferably contains a quinonediazide compound. By containing a quinonediazide compound, a positive pattern can be obtained.

[0145] Examples of the quinonediazide compound include: a compound in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound via an ester bond; a compound in which the sulfonic acid of quinonediazide is bonded to a polyamino compound via a sulfonamide bond; a compound in which the sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond; and the like. Not all functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, but preferably, on average, more than 40 mol% of the entire functional groups are substituted with quinonediazide. By using such a quinonediazide compound, a positive photosensitive resin composition that is sensitive to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, can be obtained.

[0146] Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, 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, and Tr iML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry), 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 (the above are trade names, manufactured by Asahi Organic Materials Industries), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry), Novolac resin, etc., but not limited to these.

[0147] Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl sulfide, but are not limited thereto.

[0148] Moreover, examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited thereto.

[0149] Among these, the quinonediazide compound more preferably includes an ester of a phenol compound and naphthoquinonediazide-4-sulfonyl group. This allows high sensitivity and higher resolution to be obtained in i-line exposure.

[0150] The content of the photoacid generator (c-1) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the polyimide precursor (A) to obtain sufficient sensitivity after exposure. In addition, the content of the quinonediazide compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A) to not reduce the film properties. By making the content of the quinonediazide compound within this range, it is possible to achieve further high sensitivity while obtaining the target film properties.

[0151] In addition, other photoacid generators, sensitizers, etc. such as onium salts, diaryl compounds, and iminosulfonium can be added as needed. In addition, by using an onium salt as component (B), it can also function as a photocuring agent for epoxy resin. By using an onium salt in epoxy resin, a negative pattern can be obtained. As an onium salt, for example, aromatic iodonium complex salts and aromatic sulfonium complex salts can be cited. Among them, specific examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate (manufactured by Rohdia, trade name Rhodorsil Photoinitiator 2074), and di(4-tert-butyl)iodonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF JAPAN, trade name CGI BBIC C1).

[0152] As specific examples of the aromatic sulfonium complex salt, 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro Corporation, trade name CPI-101A), 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate (manufactured by San-Apro Corporation, trade name CPI-210S), 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (manufactured by Asahi Denka Kogyo Co., Ltd., trade name SP-172), a mixture of aromatic sulfonium hexafluoroantimonate containing 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate (manufactured by Dow Chemical, trade name UVI-6976), and triphenylsulfonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF Japan, trade name CGI TPSC1), tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide (manufactured by BASF Japan Co., Ltd., trade name GSID26-1), tris[4-(4-acetylphenyl)sulfanyl]sulfonium tetrakis(pentafluorophenyl)borate (manufactured by BASF Japan Co., Ltd., trade name PAG-290), etc.

[0153] The above-mentioned (c-2) photoradical polymerization initiator is not particularly limited as long as it is a compound that generates free radicals by exposure. Alkyl phenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds and benzoate compounds are excellent in sensitivity, stability and ease of synthesis, and are therefore preferred. Among them, from the viewpoint of sensitivity, alkyl phenone compounds and oxime ester compounds are preferred, and oxime ester compounds are particularly preferred. In addition, when processing a thick film with a film thickness of more than 5 μm, from the viewpoint of resolution, phosphine oxide compounds are preferred. By containing the (c-2) photoradical polymerization initiator, a negative pattern can be obtained.

[0154] Examples of the alkylphenone compound include α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2-hydroxy-1-{4-[4- α-Hydroxyalkyl phenone compounds such as (2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one, 1-hydroxycyclohexyl-phenyl ketone, benzoin, etc., 4-benzoyl-4-methylphenyl ketone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, benzyl methoxyethyl acetal, 2,3-diethoxyacetophenone, benzyl dimethyl ketal, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., acetophenone compounds such as acetophenone and p-tert-butyldichloroacetophenone. Among these, α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one are preferred because of their high sensitivity.

[0155] Examples of the phosphine oxide compound include 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0156] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximeimino)-1-propanone, 2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime. 2-propanedione-2-(O-benzoyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), NCI-831, NCI-930 (these are manufactured by ADEKA), OXE-03, OXE-04 (these are manufactured by BASF), etc. Among these, from the viewpoint of sensitivity, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), 2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], NCI-831, NCI-930, OXE-03, and OXE-04 are preferred.

[0157] Examples of the aminobenzophenone compound include 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone.

[0158] Examples of the diketone compound include benzil.

[0159] Examples of the ketoester compound include methyl benzoylformate and ethyl benzoylformate.

[0160] Examples of the benzoate compound include methyl o-benzoylbenzoate, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and ethyl p-diethylaminobenzoate.

[0161] Other specific examples of the photoradical polymerization initiator (c-2) include benzophenone, 4-benzoyl-4'-methylphenyl ketone, dibenzyl ketone, fluorenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzyl ammonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propylammonium chloride monohydrate, thioxanthone, and 2-chlorothioxanthone. , 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propylammonium chloride, anthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methylene anthrone, 4-azidobenzylideneacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone, etc.

[0162] The content of the photoradical polymerization initiator (c-2) is preferably 0.5 to 20 parts by mass when the sum of the resin (A) and the compound having two or more ethylenically unsaturated bonds (D) described later, which is contained as required, is 100 parts by mass, because sufficient sensitivity can be obtained and the amount of outgassing during thermal curing can be suppressed. Among them, 1.0 to 10 parts by mass is more preferred.

[0163] In order to improve the function of the (c-2) photoradical polymerization initiator, the photosensitive resin composition of the present invention may contain a sensitizer. By containing a sensitizer, the sensitivity can be improved and the photosensitive wavelength can be adjusted. As the sensitizer, bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N-phenylmorpholine and their derivatives can be cited, but they are not limited to these.

[0164] In the case of a negative type, the photosensitive resin composition of the present invention may contain (D) a compound having two or more ethylenically unsaturated bonds (hereinafter, sometimes referred to as "component (D)"). By containing component (D), the crosslinking density during exposure is increased, so the exposure sensitivity is further improved. In addition, the chemical resistance of the cured film obtained by curing is further improved. In addition, by selecting a molecular structure that matches the purpose as described later, various functions such as hydrophobicity and elongation can be added.

[0165] Examples of the component (D) include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,4-butylene glycol dimethacrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, four-pentaerythritol nona(meth)acrylate, four-pentaerythritol deca(meth)acrylate, pentaerythritol undec(meth)acrylate, pentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, (2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene or 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene.

[0166] When it is desired to further improve the exposure sensitivity, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or tripentaerythritol octaacrylate is preferred. When it is desired to improve the adhesion during development due to the improvement in hydrophobicity, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is preferred. When it is desired to improve the elongation of the cured film, tetraethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate are preferred.

[0167] As the compound of other (D) components, for example, epoxy (meth) acrylate obtained by reacting a multifunctional epoxy compound with (meth) acrylic acid can be cited. Since epoxy (meth) acrylate can be added with hydrophilicity, it can be used to improve alkali developability. As the multifunctional epoxy compound, for example, the following compounds can be cited. These multifunctional epoxy compounds are excellent in heat resistance and chemical resistance, and therefore are preferred.

[0168] [Chemical formula 21]

[0169]

[0170] The molecular weight of the component (D) is preferably 5000 or less, and more preferably 2000 or less. A molecular weight of 5000 or less is preferred because compatibility with the resin (A) can be maintained and occurrence of whitening of the film can be reduced.

[0171] The content of the component (D) is preferably 5 parts by mass to 100 parts by mass, and more preferably 10 parts by mass to 50 parts by mass, relative to 100 parts by mass of the resin (A). Within this range, it is easy to obtain the effects of improving exposure sensitivity and improving chemical resistance of the cured film.

[0172] The photosensitive resin composition of the present invention may contain an antioxidant. By containing an antioxidant, the yellowing of the cured film in the subsequent heat treatment and the reduction of mechanical properties such as elongation are suppressed. In addition, the anti-rust effect on metal materials can suppress the oxidation of metal materials, so it is preferred.

[0173] As the antioxidant, hindered phenol antioxidants or hindered amine antioxidants are preferred. In addition, the number of phenolic groups or amino groups in one molecule is preferably 2 or more, more preferably 4 or more, from the viewpoint of easily obtaining an antioxidant effect.

[0174] Examples of hindered phenol antioxidants include the following, but are not limited to the following structures.

[0175] [Chemical formula 22]

[0176]

[0177] [Chemical formula 23]

[0178]

[0179] [Chemical formula 24]

[0180]

[0181] Hindered phenol antioxidants also have the effect of improving resolution because they inhibit the diffusion of free radicals. In addition, when development is performed using an alkaline aqueous solution, they function as a dissolution accelerator and also have the effect of suppressing residues.

[0182] Examples of the hindered amine antioxidant include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, and 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate. , 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, the reaction product of bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) sebacate with 1,1-dimethylethyl hydroperoxide and octane, tetrakis(1,2,2,6,6-pentamethyl-4-pyridyl)butane-1,2,3,4-tetracarboxylate or tetrakis(2,2,6,6-tetramethyl-4-pyridyl)butane-1,2,3,4-tetracarboxylate.

[0183] As other antioxidants, phenol, catechol, resorcinol, hydroquinone, 4-tert-butylcatechol, 2,6-di(tert-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol can be cited. As the amount of the antioxidant added, it is preferably 0.1 to 10.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass, relative to 100 parts by mass of the resin (A). When it is within this range, the developability and the effect of suppressing the discoloration caused by the heat treatment can be appropriately maintained.

[0184] The photosensitive resin composition of the present invention may contain a heterocyclic compound containing a nitrogen atom. By containing a heterocyclic compound containing a nitrogen atom, high adhesion can be obtained in a metal substrate that is easily oxidized, such as copper, aluminum, and silver. Although the mechanism is not clear, it is speculated that the reason is that the metal coordination ability of the nitrogen atom interacts with the metal surface, and the large volume of the heterocycle stabilizes the interaction.

[0185] Examples of the nitrogen atom-containing heterocyclic compound include imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazolidine, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyrazine, triazine, cyanuric acid, isocyanuric acid, and derivatives thereof.

[0186] More specifically, the nitrogen atom-containing heterocyclic compound includes 1H-imidazole, 1H-benzimidazole, 1H-pyrazole, indazole, 9H-carbazole, 1-pyrazoline, 2-pyrazoline, 3-pyrazoline, pyrazolidine, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylamino)-1H- ... ethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, pyridine, 1H-piperidine, dimethylpiperidine, pyrimidine, thymine, uracil, pyrazine, 1,3,5-triazine, melamine, 2, 4,6-tris(2-pyridyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl, tris((meth)acryloyloxyethyl)isocyanurate, tris(epoxypropionyloxyethyl)isocyanurate, and the like.

[0187] Among these, from the viewpoint of ease of synthesis, reactivity with metals, etc., 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H-methylbenzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, etc. are preferred.

[0188] The amount of the nitrogen-containing heterocyclic compound added is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, relative to 100 parts by mass of the resin (A). Within this range, the developability and the stabilization effect of the base metal can be appropriately maintained.

[0189] The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyramide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more kinds of these may be contained.

[0190] The content of the solvent is preferably 100 parts by mass or more based on 100 parts by mass of the (A) resin in order to dissolve the composition, and is preferably 1,500 parts by mass or less in order to form a coating film having a thickness of 1 μm or more.

[0191] If necessary, the photosensitive resin composition of the present invention may contain surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane for the purpose of improving wettability with the substrate.

[0192] In addition, in order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent as a silicon component within the range of not damaging storage stability. As the silane coupling agent, trimethoxyaminopropyl silane, trimethoxycyclohexyl epoxyethyl silane, trimethoxyvinyl silane, trimethoxythiol propyl silane, trimethoxyglycidyloxypropyl silane, tris (trimethoxysilyl propyl) isocyanurate, triethoxyaminopropyl silane, triethoxycyclohexyl epoxyethyl silane, triethoxyvinyl silane, triethoxythiol propyl silane, triethoxyglycidyloxypropyl silane, tris (triethoxysilyl propyl) isocyanurate and, trimethoxyaminopropyl silane or a reactant of triethoxyaminopropyl silane and anhydride can be cited. The reactant can be used in the state of amic acid or imidized state. Examples of the acid anhydride to be reacted include succinic anhydride, maleic anhydride, nadic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, and 4,4'-oxydiphthalic dianhydride. The preferred content of the silane coupling agent is 0.01 to 10 parts by mass relative to 100 parts by mass of the (A) resin.

[0193] Next, the shape of the photosensitive resin composition of the present invention will be described.

[0194] The photosensitive resin composition of the present invention may be in any form as long as it contains the above-mentioned (A) resin, (B) photopolymerization initiator, and (C) component, and may be in a paste or sheet form, for example.

[0195] The photosensitive sheet of the present invention is an uncured sheet material obtained by coating the photosensitive resin composition of the present invention on a support and drying it at a temperature and for a time within a range in which the solvent can be volatilized, and is soluble in an organic solvent or an alkaline aqueous solution.

[0196] The support is not particularly limited, and various films commonly available on the market, such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film, can be used. In order to improve adhesion and peelability, the bonding surface between the support and the photosensitive resin composition can be subjected to surface treatments such as silicone, silane coupling agent, aluminum chelating agent, and polyurea. In addition, the thickness of the support is not particularly limited, but is preferably within the range of 10 to 100 μm from the viewpoint of operability. In addition, in order to protect the film surface of the photosensitive composition obtained during coating, a protective film may be provided on the film surface. Thus, the surface of the photosensitive resin composition can be protected from pollutants such as garbage and dust in the atmosphere.

[0197] As a method for coating the photosensitive resin composition on the support, there can be mentioned spin coating using a spin coater, spray coating, roll coating, screen printing, methods using a knife coater, a die coater, a calender coater, a meniscus coater, a rod coater, a roll coater, a comma roll coater, a gravure roll coater, a screen coater, a slot die coater, etc. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., and generally, from the viewpoint of the uniformity of the coating film, the film thickness after drying is preferably 0.5 μm or more and 100 μm or less.

[0198] An oven, a heating plate, infrared rays, etc. can be used for drying. The drying temperature and drying time can be within the range that allows the solvent to volatilize, and are preferably appropriately set within the range in which the photosensitive resin composition becomes an uncured or semi-cured state. Specifically, it is preferably carried out within the range of 40°C to 150°C for 1 minute to several tens of minutes. In addition, these temperatures can be combined to increase the temperature in stages, for example, heat treatment can be performed at 80°C and 90°C for 2 minutes each.

[0199] Next, a method for forming a relief pattern of a cured film using the photosensitive resin composition or the photosensitive sheet of the present invention will be described.

[0200] The photosensitive resin composition of the present invention is applied to a substrate, or the photosensitive sheet is laminated to a substrate. As a substrate, a substrate plated with metal copper or a silicon wafer can be used. In addition, as a material, ceramics, gallium arsenide, etc. can be used, but are not limited to these. As a coating method, there are methods such as spin coating, spray coating, and roller coating using a spin coater. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., and is usually applied in a manner that the film thickness after drying is 0.1 to 150 μm.

[0201] In order to improve the adhesion between the substrate and the photosensitive resin composition, the substrate can be pre-treated with the above-mentioned silane coupling agent. For example, a solution of 0.5 to 20% by mass of the silane coupling agent dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is prepared. Then, the prepared solution is used to surface-treat the substrate by spin coating, dipping, spraying, steam treatment, etc. Depending on the situation, a heat treatment at 50°C to 300°C is then performed to allow the reaction between the substrate and the silane coupling agent to proceed.

[0202] Next, the substrate coated with the photosensitive resin composition or laminated with the photosensitive sheet of the present invention is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, etc., at 50° C. to 150° C. for 1 minute to several hours. It should be noted that in the case of a photosensitive sheet, it is not necessary to go through a drying step.

[0203] Next, the photosensitive resin film is exposed to chemical radiation through a mask having a desired pattern. Chemical radiation used in exposure includes ultraviolet rays, visible rays, electron beams, X-rays, etc. In the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp are preferably used.

[0204] Next, the exposed photosensitive resin film may be subjected to a post-exposure bake (PEB) step as necessary. The PEB step is preferably performed at 50° C. to 150° C. for 1 minute to several hours using an oven, a hot plate, infrared rays, or the like.

[0205] In order to form a pattern of the resin, a developer is used after exposure, and the unexposed part is removed in the case of a negative type, and the exposed part is removed in the case of a positive type. As a developer used in development, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferred. For example, in the case of a photosensitive resin composition that is insoluble in an alkaline aqueous solution, as a good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As a poor solvent, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate and water are preferred. When a good solvent is mixed with a poor solvent and used, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more solvents, such as a combination of several, may also be used.

[0206] On the other hand, in the case of a photosensitive resin composition that is soluble in an alkaline aqueous solution, the developer used in the development is a substance that dissolves and removes the polymer soluble in the alkaline aqueous solution, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved. Examples of the alkaline compound include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In addition, depending on the circumstances, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., may also be contained in these alkaline aqueous solutions alone or in combination of multiple types. After development, it is preferably rinsed with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. can also be cited. When water is used, alcohols such as ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc. can also be added to water for rinsing.

[0207] After development, a temperature of 150°C to 350°C is applied to carry out a thermal crosslinking reaction to cure it. For the heat treatment, a certain temperature can be selected and the temperature can be raised in stages, or a certain temperature range can be selected and implemented for 5 minutes to 5 hours while continuously raising the temperature. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. As the lower limit of the aging conditions in the present invention, it is preferably above 170°C, and in order to allow the curing to proceed sufficiently, it is more preferably above 180°C. In addition, the upper limit of the aging conditions is not particularly limited, and from the viewpoint of suppressing film shrinkage and stress, it is preferably below 280°C. In addition, the present invention provides a cured film that is particularly excellent in low-temperature curing properties, so it is more preferably below 250°C, and further preferably below 230°C.

[0208] The cured film formed by the photosensitive resin composition or photosensitive sheet of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, it can be suitably used for passivation films of semiconductors, surface protection films of semiconductor elements, interlayer insulating films, interlayer insulating films of multilayer wiring for high-density packaging with 2 to 10 layers, and insulating layers of organic electroluminescent elements, but it is not limited to these and various structures can be adopted. In addition, the surface of the substrate for the formation of the cured film can be appropriately selected according to the application and process, and silicon, ceramics, metals, epoxy resins, etc. can be cited, and the substrate surface can be a substrate composed of two or more of the above materials.

[0209] Next, an application example of a semiconductor device having a bump using a cured film obtained by curing the photosensitive resin composition of the present invention will be described with reference to the drawings. Figure 1 FIG. 2 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. Figure 1 As shown, on a silicon wafer 1, a passivation film 3 is formed on an aluminum (hereinafter referred to as Al) pad 2 for input and output, and a through hole is formed on the passivation film 3. An insulating film 4 is formed thereon in the form of a pattern (which is formed by curing the photosensitive resin composition of the present invention to obtain a cured film), and then a metal (Cr, Ti, etc.) film 5 is formed in a manner connected to the Al pad 2, and a metal wiring (Al, Cu, etc.) 6 is formed by electroplating or the like. The metal film 5 is etched around the solder bump 10 to insulate the pads. Barrier metal 8 and solder bump 10 are formed on the insulated pad. The cured film obtained by curing the photosensitive resin composition of the insulating film 7 can be processed into a thick film in the scribe groove 9.

[0210] In addition, when the cured film of the present invention uses a polyimide resin, it has excellent elongation at break and strength at break, so it can also relax the stress from the sealing resin during packaging, thereby preventing damage to the low dielectric constant (low-k) layer and providing a highly reliable semiconductor device.

[0211] Then, in Figure 2 The detailed method of manufacturing the semiconductor device is shown in FIG. Figure 2 As shown in FIG. 2a, an Al pad 2 for input and output is formed on a silicon wafer 1, a passivation film 3 is further formed, and an insulating film 4 is formed in the form of a pattern (which is formed by a cured film obtained by curing the photosensitive resin composition of the present invention). Next, as Figure 2 As shown in FIG. 2b, a metal (Cr, Ti, etc.) film 5 is formed in a manner connected to the Al gasket 2, such as Figure 2 As shown in FIG. 2c, the metal wiring 6 is formed into a film by electroplating. Figure 2 As shown in 2d', the photosensitive resin composition before curing of the present invention is applied and subjected to a photolithography step to form a Figure 2 The insulating film 7 is formed in a pattern as shown in FIG. 2d. At this time, the photosensitive resin composition of the insulating film 7 before curing is processed into a thick film in the scribe groove 9. If the target thickness is not achieved by one coating, multiple coatings may be performed. When a multilayer wiring structure with more than three layers is formed, the above steps may be repeated to form each layer.

[0212] Then, if Figure 22e and 2f, barrier metal 8 and solder bump 10 are formed. Then, the semiconductor device is cut along the last scribe groove 9 to be divided into individual chips. In the case where the insulating film 7 is not patterned in the scribe groove 9, or when residues remain in the scribe groove, cracks may occur during cutting, which may affect the reliability evaluation of the chip. Therefore, a technique that can provide pattern processing with excellent thick film processing, such as the present invention, is very ideal for obtaining high reliability of semiconductor devices.

[0213] Example

[0214] The present invention is described below with reference to examples, but the present invention is not particularly limited to these examples. First, the evaluation method in each example and comparative example is described. In the evaluation, a photosensitive resin composition before curing (hereinafter referred to as varnish) was used, which was filtered in advance using a polytetrafluoroethylene filter with an average pore size of 1 μm (manufactured by Sumitomo Electric Industries, Ltd.).

[0215] (1) Molecular weight determination

[0216] (A) The weight average molecular weight (Mw) of the resin was confirmed using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Waters Japan). N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was used as an eluting solvent, and the weight average molecular weight (Mw) and the degree of dispersion (PDI = Mw / Mn) in terms of polystyrene were calculated.

[0217] (2) Pattern processing

[0218] (2)-1 Sensitivity A

[0219] The varnish using polyimide resin and epoxy resin obtained in each embodiment and comparative example was spin-coated on a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then pre-baked at 120°C for 3 minutes using a hot plate (SCW-636 manufactured by Dai Nippon Screen Manufacturing Co., Ltd.) to produce a pre-baked film with a thickness of 11 μm. The obtained prebaked film was exposed in a contact manner using a parallel light mask alignment exposure machine (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Corporation) and an ultra-high pressure mercury lamp as a light source (mixed line of g-line, h-line and i-line), through a grayscale mask for sensitivity measurement (having a pattern of lines and spaces of 2 to 50 μm and 1:1. It has areas with transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50% and 60%, respectively.). Then, when the varnish is a negative type, it is baked at 120°C for 1 minute after exposure, and developed using a coating and developing device MARK-7. In the case where the polymer is not soluble in an alkaline aqueous solution, cyclopentanone is used as a developer, and spray development is performed for 2 minutes, followed by rinsing with propylene glycol monomethyl ether acetate for 30 seconds. When the polymer was dissolved in an alkaline aqueous solution, spin immersion development was performed for 90 seconds using a 2.38 mass % tetramethylammonium hydroxide (hereinafter referred to as "TMAH") aqueous solution (trade name "ELM-D", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a developer, followed by rinsing with water for 30 seconds.

[0220] The film thickness was measured after development, and the minimum exposure amount at which the residual film ratio of the exposed part exceeded 90% was taken as the sensitivity. The exposure amount was measured using an I-line illuminometer.

[0221] The film thickness was measured at a refractive index of 1.629 using Lambda STM-602 manufactured by Dai Nippon Screen Mfg. Co., Ltd. The same applies to the film thickness described below.

[0222] (2)-2 Sensitivity B

[0223] The varnish using the polysiloxane obtained in each example and comparative example was spin-coated on a 10 cm square alkali-free glass substrate using a spin coater and pre-baked at 90° C. for 2 minutes using a hot plate to prepare a pre-baked film having a thickness of 2 μm.

[0224] The prepared prebaked film was exposed in a contact manner using a PLA-501F and an ultra-high pressure mercury lamp as a light source (a mixed line of g-line, h-line, and i-line) through a grayscale mask for sensitivity measurement (a pattern of lines and spaces of 2 to 50 μm and 1:1. It has areas with transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%, respectively.). Then, an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Industry Co., Ltd.) was used to perform shower development for 100 seconds using a 0.045 mass % potassium hydroxide aqueous solution or 2.38 mass % TMAH, followed by rinsing with water for 30 seconds. After development, the film thickness was measured, and the minimum exposure amount at which the residual film rate of the exposed part exceeded 90% was taken as the sensitivity. The exposure was measured using an I-line illuminometer.

[0225] The film thickness was measured at a refractive index of 1.550 using Lambda STM-602 manufactured by Dai Nippon Screen Mfg. Co., Ltd. The same applies to the film thickness described below.

[0226] (2)-3 Development A

[0227] The minimum pattern size after development at the exposure amount of sensitivity A defined in (2)-1 was measured.

[0228] (2)-4 Development B

[0229] The minimum pattern size after development at the exposure amount of sensitivity B defined in (2)-2 was measured.

[0230] (3) Evaluation of chemical resistance

[0231] (3)-1 Chemical resistance evaluation A

[0232] Using a coating and developing device MARK-7, a varnish (using the polyimide resin and epoxy resin obtained in each embodiment and comparative example) was applied to a silicon wafer by spin coating so that the film thickness after pre-baking at 120°C for 3 minutes would be 10 μm. After pre-baking, in the case of a negative type, PLA-501F was used to coat the entire surface at 300 mJ / cm 2Exposure was performed. In the case of positive type, the inert oven CLH-21CD-S was used directly, and the temperature was raised to 180°C at a rate of 3.5°C per minute under a nitrogen flow at an oxygen concentration of less than 20 ppm. The temperature was heated at each temperature for 1 hour. When the temperature reached less than 50°C, the silicon wafer was taken out, and the cured film was immersed in an organic liquid (dimethyl sulfoxide: 25 mass % TMAH aqueous solution = 92:2) at 40°C for 10 minutes, and the peeling of the pattern and the change in film thickness (indicating swelling or elution amount) were observed. As a result, the case where the pattern was not peeled and the film thickness changed by less than 5% was evaluated as 4, the case where the pattern was not peeled and the film thickness changed by more than 5% and less than 10% was evaluated as 3, the case where the pattern was not peeled and the film thickness changed by more than 10% and less than 30% was evaluated as 2, and the case where the pattern was peeled, no film remained, and the film thickness changed by more than 30% was evaluated as 1.

[0233] The less the pattern peels off and the smaller the change in film thickness is, the better the chemical resistance is.

[0234] (3)-2 Chemical resistance evaluation B

[0235] Using a spin coater, a varnish (using the polysiloxane obtained in each embodiment and comparative example) was spin-coated on a glass substrate (hereinafter referred to as an "ITO substrate") having an ITO sputtered on the surface, and pre-baked at 100°C for 2 minutes using a hot plate (trade name SCW-636, manufactured by Dai Nippon Screen Manufacturing Co., Ltd.) to produce a film with a thickness of 2.0 μm.

[0236] PLA-501F was used for the prepared film at 300 mJ / cm 2 The exposure was performed and the film was aged in air at 170° C. for 1 hour using an oven (trade name: IHPS-222, manufactured by ESPEC Corporation) to produce a cured film.

[0237] The obtained cured film was immersed in resist stripping liquid N300 at 50°C for 3 minutes, and the pattern peeling and the change in film thickness (indicating swelling or elution amount) were observed. The results were evaluated in the same manner as in the above (3)-1 Chemical Resistance Evaluation A.

[0238] (4) Determination of elongation at breaking point and strength at breaking point

[0239] The varnish (using the polyimide and epoxy resin obtained in each embodiment and comparative example) was applied on a 6-inch silicon wafer by spin coating using a coating and developing device ACT-8, and pre-baked so that the film thickness after pre-baking at 120°C for 3 minutes was 11 μm. Then, in the case of a negative type, PLA was used and the entire surface was treated with 300 mJ / cm 2Exposure is performed. In the case of positive type, an inert oven CLH-21CD-S (manufactured by Koyo Thermo System (co., Ltd.) is directly used, and the temperature is raised to 180°C at 3.5°C / min at an oxygen concentration of less than 20ppm, and a heating treatment is performed at each temperature for 1 hour. When the temperature becomes less than 50°C, the silicon wafer is taken out and immersed in 45% by mass hydrofluoric acid for 5 minutes, thereby peeling off the cured film of the resin composition from the wafer. The film is cut into strips with a width of 1.5cm and a length of 9cm, and is stretched at a tension rate of 50mm / min (chuck spacing = 2cm) using Tensilon RTM-100 (manufactured by Orientech (co., Ltd.) at a room temperature of 23.0°C and a humidity of 45.0%RH, and the elongation at break (%) and the strength at break (MPa) are measured. For each sample to be tested, 10 strips are measured, and the average value of the 5 results with the largest values ​​is calculated based on the results (significant figures = 2 digits). This evaluation was carried out as an evaluation of the mechanical properties of polyimide and epoxy resin.

[0240] (5) Evaluation of copper substrate adhesion

[0241] (5)-1 Evaluation of copper substrate adhesion A

[0242] Adhesion with metal copper was evaluated by the following method.

[0243] First, the varnish was applied to a copper-plated substrate with a thickness of about 3 μm by spin coating, and then baked on a hot plate (Dai Nippon Screen Manufacturing Co., Ltd. D-SPIN) at 120°C for 3 minutes to prepare a pre-baked film with a final thickness of 8 μm. In the case of negative type, PLA was used and the entire surface was heated at 300 mJ / cm 2Exposure was performed, and in the case of positive type, the film was directly subjected to an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) and heated to 230°C at a rate of 3.5°C / min at an oxygen concentration of less than 20 ppm, and then subjected to a heat treatment at 230°C for 1 hour. When the temperature reached less than 50°C, the substrate was taken out and divided into two parts. For each substrate, a single-edged knife was used to carve 10 rows and 10 columns of checkerboard-like grooves at intervals of 2 mm on the cured film. Using one of the sample substrates, the bonding properties between the metal material and the cured resin film were evaluated by peeling based on "Cellotape" (registered trademark) according to how many squares out of 100 squares peeled off. In addition, for another sample substrate, a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai Espekic Co., Ltd.) was used to perform a PCT treatment for 400 hours under saturated conditions of 121°C and 2 atmospheres, and then the above-mentioned peeling test was performed. For any substrate, the evaluation was performed as follows: the case where the number of peelings in the peeling test was 0 was set to 5, the case where the number of peelings was 1 or more and less than 10 was set to 4, the case where the number of peelings was 10 or more and less than 30 was set to 3, the case where the number of peelings was 30 or more and less than 50 was set to 2, and the case where the number of peelings was 50 or more was set to 1.

[0244] The smaller the number of peelings, the better the adhesion.

[0245] (5)-2 Evaluation of copper substrate adhesion B

[0246] In the same manner as described in (3)-2 above, a cured film with a film thickness of 2.0 μm is formed on a copper substrate. The obtained substrate is divided into two, and for each substrate, a single-edged knife is used to carve 10 rows and 10 columns of checkerboard-like grooves at intervals of 2 mm on the cured film. Using one of the sample substrates, the bonding properties between the metal material / resin cured film are evaluated by peeling based on "Cellotape" (registered trademark) based on how many squares out of 100 squares peel off. In addition, for another sample substrate, a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai Espekic (Co., Ltd.) is used to perform PCT treatment for 25 hours at 85°C and 85%, and then the above-mentioned peeling test is performed. The determination of the adhesion is carried out in the same manner as the above-mentioned (5)-1 copper substrate adhesion evaluation A.

[0247] (6) Determination of imidization rate

[0248] The imidization rate (%) of the cured film can be easily determined by the following method. The same steps as (4) are carried out until the heat treatment to prepare a cured film on a silicon wafer. Next, the infrared absorption spectrum of the prepared cured film is measured (with the silicon wafer as the baseline), and the absorption peak (1780 cm-1) of the imide structure of the polyimide is confirmed. -1 Nearby, 1377cm -1 nearby), find 1377cm -1 Next, the cured film was heat treated at 350°C for 1 hour, and the infrared absorption spectrum was measured to determine the peak intensity (X) at 1377 cm -1 The peak intensity ratios of these peaks correspond to the content of the imide groups in the polymer before the heat treatment, that is, the imidization ratio (imidization ratio = X / Y×100 (%)).

[0249] (7) Storage stability of varnish

[0250] The viscosity of the varnish after preparation and the viscosity after leaving it at 23° C. for 2 weeks were measured, and the rate of change in viscosity before and after leaving it was calculated.

[0251] The smaller the change rate of the viscosity before and after standing, the better the storage stability.

[0252] (8) Hardness

[0253] On the ITO substrate, a cured film having a thickness of 2.0 μm was formed in the same manner as described in (3)-2 above. The pencil hardness of the obtained cured film was measured in accordance with JIS "K5600-5-4 (establishment date = 1999 / 04 / 20)". This evaluation was carried out as an evaluation of the mechanical properties of polysiloxane.

[0254] (9) Coefficient of thermal expansion (CTE)

[0255] A self-supporting film of the cured film was prepared by the same procedure as in (4), and the film was cut into 3.0 cm × 0.5 cm with a single-edged knife. The temperature was raised from 25°C to 400°C at a rate of 10°C / min under a nitrogen flow of 80 mL / min using a differential scanning calorimeter (TMA / SS6100 manufactured by Seiko Instruments). The linear expansion coefficient from 50°C to 150°C was calculated as CTE (10 -6 / K).

[0256] [Synthesis Example 1 Synthesis of polyimide precursor (P-1)]

[0257] 31.02 g (0.10 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was added to a 500 ml separable flask, 26.03 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA) and 76 ml of γ-butyrolactone were added, and 16.22 g (0.21 mol) of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the exotherm caused by the reaction was terminated, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

[0258] Next, under ice cooling, a solution of 41.27 g (0.2 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 140 mL of γ-butyrolactone was stirred, and the reaction mixture was added over 20 minutes. Next, 18.62 g (0.093 mol) of 4,4'-diaminodiphenyl ether (DAE) was added in 5 portions over 20 minutes while stirring. Furthermore, after stirring at room temperature for 2 hours, 6 ml of ethanol (EtOH) was added, stirred for 1 hour, and then 65 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0259] The obtained reaction solution was added to 800 ml of EtOH to generate a precipitate containing a crude polymer. The generated crude polymer was filtered and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 6 L of water to precipitate the polymer, and the precipitate was collected by filtration. After washing with water 3 times, it was vacuum dried to obtain a powdered polyimide precursor (P-1). The molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 31000 and the PDI was 2.6. The polyimide precursor (P-1) was insoluble in alkaline aqueous solution, and the photosensitive resin composition using the polyimide precursor (P-1) was developed using cyclopentanone. Table 1 summarizes the molar ratios of the constituent components of the polyimide precursors of Synthesis Examples 1 to 4 and the polysiloxanes of Synthesis Examples 5 and 6.

[0260] [Synthesis Example 2: Synthesis of polyimide precursor (P-2)]

[0261] Under a dry nitrogen stream, 62.04 g (0.2 mol) of ODPA was dissolved in 1000 g of NMP. 96.72 g (0.16 mol) of diamine (HA) of the following structure and 4.97 g (0.02 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were added together with 100 g of NMP, and reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.37 g (0.04 mol) of 3-aminophenol (MAP) as a terminal blocking agent was added together with 30 g of NMP, and reacted at 50°C for 2 hours. Then, the following solution was added dropwise over 10 minutes, wherein the solution was prepared by diluting 47.66 g (0.4 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then the solution was put into 1L of water to obtain a precipitate. The precipitate was collected by filtration, washed with water 3 times, and dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of the polyimide precursor resin (P-2). The molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 25,000 and the PDI was 2.3. The polyimide precursor (P-2) is soluble in alkaline aqueous solution, and the photosensitive resin composition using the polyimide precursor (P-2) is developed using a 2.38% by mass TMAH aqueous solution.

[0262] [Chemical formula 25]

[0263]

[0264] [Synthesis Example 3: Synthesis of polyimide precursor (P-3)]

[0265] A polyimide precursor (P-3) was obtained in the same manner as in Synthesis Example 1 except that 29.42 g of biphenyltetracarboxylic anhydride (BPDA) was used instead of ODPA. The Mw of the polyimide precursor (P-3) was 34,000, and the PDI was 2.5. The polyimide precursor (P-3) was developed with cyclopentanone.

[0266] [Synthesis Example 4: Synthesis of polyimide precursor (P-4)]

[0267] A polyimide precursor (P-4) was obtained in the same manner as in Synthesis Example 1 except that 18.03 g (0.090 mol) of DAE and 0.80 g (0.002 mol) of 1,3,5-tris(4-aminophenoxy)benzene (TAPOB) were used instead of 18.62 g of DAE. The polyimide precursor (P-4) had an Mw of 27,000 and a PDI of 2.9. The polyimide precursor (P-4) was developed with cyclopentanone.

[0268] [Synthesis Example 5 Synthesis of polysiloxane (P-5) solution]

[0269] Into a 500 ml three-necked flask, 43.74 g (0.195 mol) of p-styryltrimethoxysilane (St), 14.06 g (0.06 mol) of γ-acryloylpropyltrimethoxysilane (Acry), 11.80 g (0.045 mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.173 g of TBC, and 74.58 g of PGME were placed, and an aqueous solution of phosphoric acid in which 0.348 g (corresponding to 0.50% by mass of the charged monomer) of phosphoric acid was dissolved in 17.01 g of water was added over 30 minutes while stirring at room temperature. Then, the three-necked flask was immersed in an oil bath at 70° C., stirred for 90 minutes, and then the temperature of the oil bath was raised to 115° C. over 30 minutes. One hour after the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and heating and stirring were started for 2 hours (internal temperature was 100-110°C) to obtain a polysiloxane solution. It should be noted that nitrogen was introduced at 0.05L / min during heating and heating and stirring. During the reaction, a total of 36.90g of methanol and water as by-products were distilled out. PGME was added to the obtained polysiloxane solution to make the solid content concentration 40% by mass to obtain a polysiloxane (P-5) solution.

[0270] [Synthesis Example 6 Synthesis of polysiloxane (P-6) solution]

[0271] Into a 500 ml three-necked flask, 44.86 g (0.200 mol) of p-phenyltrimethoxysilane (St), 39.66 g (0.200 mol) of phenyltrimethoxysilane (Ph), 6.81 g (0.050 mol) of methyltrimethoxysilane (Me), 13.12 g (0.050 mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.522 g of TBC, and 74.58 g of PGME were placed, and while stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.448 g (0.50 mass % relative to the charged monomers) of phosphoric acid in 27.90 g of water was added over 30 minutes. Then, the three-necked flask was immersed in an oil bath at 70° C., stirred for 90 minutes, and then the oil bath was heated to 115° C. over 30 minutes. One hour after the start of heating, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and heating and stirring were started for 2 hours (internal temperature was 100-110°C) to obtain a polysiloxane solution. It should be noted that nitrogen was introduced at 0.05L / min during heating and heating and stirring. During the reaction, a total of 58.90g of methanol and water as by-products were distilled out. PGME was added to the obtained polysiloxane solution to make the solid content concentration 40% by mass to obtain a polysiloxane (P-6) solution.

[0272] [Table 1]

[0273]

[0274] The alkali generating agents used in Examples and Comparative Examples are shown below.

[0275] BI: 2-(9-oxoxanthene-2-yl)propanoic acid-1,5,7-triazabicyclo[4.4.0]dec-5-ene

[0276] [Chemical formula 26]

[0277]

[0278] B-II: 2-(3-Benzoylphenyl)guanidine propionate

[0279] [Chemical formula 27]

[0280]

[0281] B-III: Compound with the following structure

[0282] [Chemical formula 28]

[0283]

[0284] B-IV: Compounds with the following structures

[0285] [Chemical formula 29]

[0286]

[0287] BV: Compound with the following structure

[0288] [Chemical formula 30]

[0289]

[0290] B-VI: Compounds with the following structures

[0291] [Chemical formula 31]

[0292]

[0293] B-VII: Compound of the following structure

[0294] [Chemical formula 32]

[0295]

[0296] B-VIII: Compounds of the following structures

[0297] [Chemical formula 33]

[0298]

[0299] B-IX: Compound with the following structure

[0300] [Chemical formula 34]

[0301]

[0302] BX: N-tert-Butyloxycarbonyldimethylpiperidin

[0303] [Chemical formula 35]

[0304]

[0305] [Example 1]

[0306] Under a yellow light, 10.00 g of a polyimide precursor (P-1), 0.50 g of 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] ("Irgacure OXE-01 (trade name)", manufactured by BASF), 0.30 g of BI, 2.00 g of NK ESTER 4G (trade name) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., chemical name: tetraethylene glycol dimethacrylate), 0.2 g of N-phenyldiethanolamine, and 0.30 g of 3-trimethoxysilyl-o-aminobenzoic acid were dissolved in 15.15 g of N-methylpyrrolidone (NMP) and 3.81 g of ethyl lactate (EL), and 0.10 g of a 1 mass % EL solution of "Polyflow 77 (trade name)" (manufactured by Kyoeisha Chemical Co., Ltd.) as an acrylic surfactant was added and stirred to obtain a varnish. The characteristics of the obtained varnish were measured by the above-mentioned evaluation method, and the pattern processing properties (sensitivity A, developability A), chemical resistance A, elongation at break, strength at break, thermal linear expansion coefficient, copper substrate adhesion evaluation A, imidization ratio and storage stability were measured.

[0307] [Example 2]

[0308] The same procedure as in Example 1 is carried out except that BI is replaced by B-II.

[0309] [Example 3]

[0310] The same procedure as in Example 1 was carried out except that BI was replaced by B-III.

[0311] [Example 4]

[0312] The same procedure as in Example 1 was carried out except that BI was replaced by B-IV.

[0313] [Example 5]

[0314] The same procedure as in Example 1 is carried out except that BI is replaced by BV.

[0315] [Example 6]

[0316] The same procedure as in Example 1 is carried out except that BI is replaced by B-VI.

[0317] [Example 7]

[0318] The same procedure as in Example 1 was carried out except that BI was replaced by B-VII.

[0319] [Example 8]

[0320] The same procedure as in Example 1 was carried out except that BI was replaced by B-VIII.

[0321] [Example 9]

[0322] The same procedure as in Example 1 was carried out except that BI was replaced by B-IX.

[0323] [Example 10]

[0324] The same procedure as in Example 3 was carried out except that P-1 was replaced by P-3.

[0325] [Example 11]

[0326] The same procedure as in Example 3 was carried out except that P-1 was replaced by P-4.

[0327] [Example 12]

[0328] The same procedure as in Example 3 was carried out except that the amount of B-III added was changed to 0.01 g.

[0329] [Example 13]

[0330] The same procedure as in Example 3 was carried out except that the amount of B-III added was changed to 0.03 g.

[0331] [Example 14]

[0332] The same procedure as in Example 3 was carried out except that the amount of B-III added was changed to 0.7 g.

[0333] [Example 15]

[0334] The same procedure as in Example 3 was carried out except that the amount of B-III added was changed to 1.0 g.

[0335] [Example 16]

[0336] The same procedure as in Example 3 was carried out except that the amount of B-III added was changed to 2.0 g.

[0337] [Example 17]

[0338] Under a yellow light, 10.00 g of a polyimide precursor (P-1), 0.80 g of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone ("Irgacure 379 (trade name)" manufactured by BASF), 0.2 g of diethylthioxanthone, 0.30 g of B-III, 2.00 g of 4G, 0.2 g of N-phenyldiethanolamine, and 0.30 g of 3-trimethoxysilyl-o-aminobenzoic acid were dissolved in 15.15 g of NMP and 3.81 g of EL, and 0.10 g of a 1% by mass EL solution of Polyflow 77 was added, followed by stirring to obtain a varnish. The characteristics of the obtained varnish were measured by the above-mentioned evaluation methods, including pattern processability (sensitivity A, developability A), chemical resistance A, elongation at break, strength at break, thermal linear expansion coefficient, copper substrate adhesion evaluation A, imidization ratio and storage stability.

[0339] [Example 18]

[0340] The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure 819 (trade name)", manufactured by BASF).

[0341] [Example 19]

[0342] The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ("Irgacure 127 (trade name)", manufactured by BASF).

[0343] [Example 20]

[0344] The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with ethyl p-dimethylaminobenzoate.

[0345] [Example 21]

[0346] The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with 4-phenylbenzophenone.

[0347] [Example 22]

[0348] The same procedures as in Example 1 were carried out except that a solid polyfunctional aromatic epoxy resin (YDCN-700-10 (trade name), manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) which is a cresol Novolac type polyfunctional epoxy resin was used instead of the polyimide precursor (P-1) and 2 g of dipentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) was further added. However, only the imidization rate was not measured.

[0349] [Example 23]

[0350] Under a yellow light, 10.00 g of the polyimide precursor (P-2), 2.0 g of TP5-280M (Toyo Gosei; TrisP-PA (Honshu Chemical) naphthoquinone diazide-5-sulfonate compound), and 0.2 g of BI were dissolved in 14.5 g of NMP, and 0.10 g of a 1 wt% NMP solution of Polyflow 77 was added and stirred to obtain a varnish. The properties of the obtained varnish were measured using the above-mentioned evaluation method.

[0351] [Example 24]

[0352] The same procedure as in Example 23 was carried out except that BI was replaced by B-II.

[0353] [Example 25]

[0354] The same procedure as in Example 23 was carried out except that BI was replaced by B-III.

[0355] [Example 26]

[0356] The same procedure as in Example 23 was carried out except that BI was replaced by B-IV.

[0357] [Example 27]

[0358] The same procedure as in Example 23 was carried out except that BI was replaced by BV.

[0359] [Example 28]

[0360] The same procedure as in Example 23 was carried out except that BI was replaced by B-VI.

[0361] [Example 29]

[0362] The same procedure as in Example 23 was carried out except that BI was replaced by B-VII.

[0363] [Example 30]

[0364] The same procedure as in Example 23 was carried out except that BI was replaced by B-VIII.

[0365] [Example 31]

[0366] The same procedure as in Example 23 was carried out except that BI was replaced by B-IX.

[0367] [Example 32]

[0368] The same procedure as in Example 25 was carried out except that the amount of B-III added was changed to 0.01 g.

[0369] [Example 33]

[0370] The same procedure as in Example 25 was carried out except that the amount of B-III added was changed to 0.03 g.

[0371] [Example 34]

[0372] The same procedure as in Example 25 was carried out except that the amount of B-III added was changed to 0.7 g.

[0373] [Example 35]

[0374] The same procedure as in Example 25 was carried out except that the amount of B-III added was changed to 1.0 g.

[0375] [Example 36]

[0376] The same procedure as in Example 25 was carried out except that the amount of B-III added was changed to 1.5 g.

[0377] [Example 37]

[0378] Under a yellow light, 0.080 g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime) ("Irgacure" (registered trademark) OXE-02 (trade name), manufactured by BASF Japan), 0.160 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure" (registered trademark)-819 (trade name), manufactured by BASF Japan), 0.200 g of a PGME 10 mass % solution of ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] ("IRGANOX" (registered trademark)-245 (trade name), manufactured by BASF Japan), and 0.200 g of a PGME 10 mass % solution of pentaerythritol acrylate ("Light 0.800 g of "Acrylate" (registered trademark) PE-3A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.), 0.16 g of BI, and 0.120 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in a mixed solvent of 8.615 g of PGME and 3.200 g of PGMEA, and 0.020 g (equivalent to a concentration of 100 ppm) of a PGME 10 mass % diluted solution of a silicone surfactant (trade name "BYK" (registered trademark) -333, manufactured by BYK Chemie Japan Co., Ltd.) was added and stirred. Then, 6.645 g of a polysiloxane (P-5) solution as (A) polysiloxane was added, followed by filtration with a 0.45 μm filter to obtain a varnish containing polysiloxane. The obtained varnish was evaluated for the sensitivity B, developability B, chemical resistance B, hardness, copper substrate adhesion B, and storage stability described above.

[0379] [Example 38]

[0380] The same procedure as in Example 37 was carried out except that BI was replaced by B-II.

[0381] [Example 39]

[0382] The same procedure as in Example 37 was carried out except that BI was replaced by B-III.

[0383] [Example 40]

[0384] The same procedure as in Example 37 was carried out except that BI was replaced by B-IV.

[0385] [Example 41]

[0386] The same procedure as in Example 37 was carried out except that BI was replaced by BV.

[0387] [Example 42]

[0388] The same procedure as in Example 37 was carried out except that BI was replaced by B-VI.

[0389] [Example 43]

[0390] The same procedure as in Example 37 was carried out except that BI was replaced by B-VII.

[0391] [Example 44]

[0392] The same procedure as in Example 37 was carried out except that BI was replaced by B-VIII.

[0393] [Example 45]

[0394] The same procedure as in Example 37 was carried out except that BI was replaced by B-IX.

[0395] [Example 46]

[0396] Under a yellow light, 0.240 g of TP5-280M (manufactured by Toyo Gosei; naphthoquinone diazide-5-sulfonate compound of TrisP-PA (manufactured by Honshu Chemical)), 0.160 g of BI, and 0.120 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in a mixed solvent of 7.565 g of PGME and 3.200 g of PGMEA, and 0.020 g (equivalent to a concentration of 100 ppm) of a PGME 10 mass % dilution solution of a silicone surfactant (trade name "BYK" (registered trademark)-333, manufactured by BYK Chemie Japan Co., Ltd.) was added and stirred. Then, 8.695 g of a polysiloxane (P-6) solution as (A) polysiloxane was added, followed by filtration with a 0.45 μm filter to obtain a varnish. The obtained varnish was evaluated for the sensitivity B, developability B, chemical resistance B, hardness, copper substrate adhesion B, and storage stability described above.

[0397] [Example 47]

[0398] The same procedure as in Example 46 was carried out except that BI was replaced by B-II.

[0399] [Example 48]

[0400] The same procedure as in Example 46 was carried out except that BI was replaced by B-III.

[0401] [Example 49]

[0402] The same procedure as in Example 46 was carried out except that BI was replaced by B-IV.

[0403] [Example 50]

[0404] The same procedure as in Example 46 was carried out except that BI was replaced by BV.

[0405] [Example 51]

[0406] The same procedure as in Example 46 was carried out except that BI was replaced by B-VI.

[0407] [Example 52]

[0408] The same procedure as in Example 46 was carried out except that BI was replaced by B-VII.

[0409] [Example 53]

[0410] The same procedure as in Example 46 was carried out except that BI was replaced by B-VIII.

[0411] [Example 54]

[0412] The same procedure as in Example 46 was carried out except that BI was replaced by B-IX.

[0413] [Comparative Example 1]

[0414] The same implementation as in Example 1 is carried out except that BI is replaced by BX.

[0415] [Comparative Example 2]

[0416] The same procedure as in Example 3 was carried out except that OXE-01 was not added.

[0417] [Comparative Example 3]

[0418] The same procedure as in Example 1 was carried out except that BI was not added.

[0419] [Comparative Example 4]

[0420] The same procedure as in Example 23 is carried out except that BI is replaced by BX.

[0421] [Comparative Example 5]

[0422] The same procedure as in Example 25 was carried out except that TP5-280M was not added.

[0423] [Comparative Example 6]

[0424] The same procedure as in Example 23 was carried out except that BI was not added.

[0425] [Comparative Example 7]

[0426] The same procedure as in Example 22 was carried out except that B-III was not added.

[0427] [Comparative Example 8]

[0428] The same procedure as in Example 37 is carried out except that BI is replaced by BX.

[0429] [Comparative Example 9]

[0430] The same procedure as in Example 39 was carried out except that IC-819 and OXE-02 were not added.

[0431] [Comparative Example 10]

[0432] The same procedure as in Example 37 was carried out except that BI was not added.

[0433] [Comparative Example 11]

[0434] The same procedure as in Example 46 is carried out except that BI is replaced by BX.

[0435] [Comparative Example 12]

[0436] The same procedure as in Example 48 was carried out except that TP5-280M was not added.

[0437] [Comparative Example 13]

[0438] Except not adding BI, it implemented similarly to Example 46. The results of Example and Comparative Example are shown in the following table.

[0439] [Table 2-1]

[0440]

[0441] [Table 2-2]

[0442]

[0443] [Table 3]

[0444] [Table 3]

[0445]

[0446] [Table 4]

[0447] [Table 4]

[0448]

[0449] [Table 5]

[0450]

[0451] [Table 6]

[0452]

[0453] [Table 7]

[0454]

[0455] [Table 8]

[0456]

[0457] [Table 9]

[0458]

[0459] [Table 10]

[0460]

[0461] Description of Reference Numerals

[0462] 1 Silicon Wafer

[0463] 2 Al gasket

[0464] 3 Passivation film

[0465] 4 Insulation film

[0466] 5 Metal (Cr, Ti, etc.) film

[0467] 6 Metal wiring (Al, Cu, etc.)

[0468] 7 Insulation film

[0469] 8 Barrier Metals

[0470] 9 Scribe Line

[0471] 10 Solder Bumps

Claims

1. A photosensitive resin composition comprising: (A) a resin comprising a polyimide precursor or a polysiloxane; (B) a thermal base generator; and (C) a photosensitizer, wherein the thermal base generator (B) comprises a guanidine derivative and / or a biguanide derivative, and the photosensitizer (C) comprises (c-1) a photoacid generator and / or (c-2) a photoradical polymerization initiator, The content of the thermal base generator (B) is 2 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the resin (A), The (B) thermal base generating agent contains a compound represented by the general formula (1), In the general formula (1), R 1 ~R 7 each independently represents a hydrogen atom or a substituted or unsubstituted group which is an alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or an arylalkyl group having 7 to 50 carbon atoms, Z - is the general formula (5), In the general formula (5), R 30 represents a substituted or unsubstituted group selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an alkenyl group having 2 to 50 carbon atoms, an alkynyl group having 2 to 50 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, an arylalkynyl group having 7 to 15 carbon atoms, a furyl group, a thienyl group or a pyrrolyl group, R 31 ~R 33 It represents a substituted or unsubstituted aryl group having 6 to 50 carbon atoms.

2. The photosensitive resin composition according to claim 1, wherein The (A) resin contains a polyimide precursor having a biphenyl structure.

3. The photosensitive resin composition according to claim 1 or 2, wherein The (A) resin contains a polyimide precursor having a residue of an amino compound having a valence of three or more.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (C) photosensitizer contains (c-1) a photoacid generator.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (C) photosensitive agent contains (c-2) a photoradical polymerization initiator, and the (c-2) photoradical polymerization initiator contains any one or more selected from the group consisting of alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, oxime ester compounds and benzoate compounds. 6 . A photosensitive sheet comprising the photosensitive resin composition according to claim 1 . 7 . A cured film obtained by curing the photosensitive resin composition according to claim 1 or the photosensitive sheet according to claim 6 .

8. A method for producing a cured film, comprising the following steps: a step of applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate, or laminating the photosensitive sheet according to claim 6 on a substrate, and drying to form a photosensitive resin film; a step of exposing the photosensitive resin film; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film.

9. The method for producing a cured film according to claim 8, wherein: The step of heat-treating the developed photosensitive resin film includes the step of heat-treating the film at 170° C. or higher and 280° C. or lower. 10 . An electronic component having a relief pattern of the cured film according to claim 7 .

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