JP7409087B2 - Photosensitive resin compositions, photosensitive sheets, cured films thereof, manufacturing methods thereof, electronic components - Google Patents

Description

The present invention relates to a photosensitive resin composition, a photosensitive sheet, a cured film thereof, a manufacturing method thereof, and an electronic component. More specifically, photosensitive resin compositions, photosensitive sheets, cured films thereof and methods for producing the same, electronic Regarding parts.

A photosensitive material that can be patterned and has excellent heat resistance and electrical insulation properties, and is a typical material for surface protection films and interlayer insulating films of semiconductor devices, insulating layers of organic electrolytic devices, and flattening films of TFT substrates. Examples include polyimide resins. In recent years, as part of efforts to increase semiconductor integration, semiconductor devices that form multilayer metal rewiring have been attracting attention. When forming such multilayer metal rewiring, efforts are being made to lower the curing temperature of the insulating film in order to reduce warping of the base material.

Further, highly transparent and highly hard photosensitive polysiloxanes are being considered as protective films for devices including display devices such as touch panels. Here too, there is a growing need to protect base materials with low heat resistance, and low-temperature curing of polysiloxane is desired.

In response to such low-temperature curing needs, for example, photosensitive polyimides can be cured at low temperatures by combining a soluble polyimide that has been imidized in advance and a crosslinking agent (Patent Document 1), and pattern processing using a photobase generator. A method of lowering the thermosetting temperature by imidization (Patent Document 2) is being considered. Furthermore, as a photosensitive polysiloxane, a method of combining a siloxane having a highly reactive polymerizable group with a polymerization initiator is being considered. (Patent Document 3)

International Publication No. 2004/109403 Japanese Patent Application Publication No. 2010-133996 JP 2017-8147 Publication

Against this social background, there is a need for technology for curing photosensitive insulating materials such as polyimide and polysiloxane at low temperatures. However, for example, with the technique of Patent Document 1, it is difficult to achieve both chemical resistance and crack resistance of the cured film, and with the technique of Patent Document 2, exposure sensitivity is low, and each has problems with reliability and takt time. Furthermore, with regard to polysiloxane, the technique of Patent Document 3 has problems in that sufficient film hardness cannot be obtained and storage stability is also poor.

The present invention solves the problems associated with the conventional technology as described above, and enables the formation of good patterns using a general photolithography process. The present invention provides a photosensitive resin composition with excellent properties.

In order to solve the above problems, the present invention relates to the following.

That is, (A) any one or more resin selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polysiloxane, (B) thermal base generator, (C ) A photosensitive resin composition containing 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. The present invention relates to a photosensitive resin composition containing a radical photopolymerization initiator and/or (c-2) a radical photopolymerization initiator.

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

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

Further, a step of applying the photosensitive resin composition onto a substrate or laminating the photosensitive sheet onto the substrate and drying it to form a photosensitive resin film, and a step of exposing the photosensitive resin film to light. , relating to a method for producing a cured film, including the steps of heat-treating a photosensitive resin film after exposure, developing the photosensitive resin film after heat treatment, and heat-treating the photosensitive resin film after development. .

The present invention also relates to an electronic component having a relief pattern of the cured film.

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 temperatures has excellent chemical resistance, adhesion, and mechanical properties. Furthermore, the electronic component of the present invention has a pattern with excellent adhesiveness and chemical resistance, and is highly reliable.

FIG. 2 is a diagram showing an enlarged cross section of a pad portion of a semiconductor device having bumps. FIG. 3 is a diagram showing a detailed method for manufacturing a semiconductor device having bumps.

The present invention provides (A) any one or more resins selected from the group consisting of epoxy resins, polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, and polysiloxanes, (B) a thermal base generator, and (C) A photosensitive resin composition containing 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 photosensitive resin composition. Provided is a photosensitive resin composition containing an acid generator and/or (c-2) a radical photopolymerization initiator. Each component will be explained below.

The photosensitive resin composition of the present invention contains (A) any one or more resin selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polysiloxane. (Hereinafter, it may be abbreviated as "(A) resin"). Among these, it is preferable to contain a polyimide precursor or polysiloxane. (A) Examples of the polyimide precursor used for the resin include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. A polyamic acid having a tetracarboxylic acid residue and a diamine residue can be obtained by reacting an acid component and a diamine component.
Here, examples of the acid component include tetracarboxylic acid, tetracarboxylic dianhydride, and tetracarboxylic diester dichloride. Examples of the diamine component include diamines, diisocyanate compounds, and trimethylsilylated diamines.

(A) As the polyimide precursor of the resin, a resin containing a structural unit represented by the following general formula (6) is preferable. Further, it may contain two or more types of resins having this structural unit, or it may be a copolymerization of two or more types of structural units. Among these, for the purpose of lowering the linear thermal expansion coefficient while maintaining exposure sensitivity, a polyimide precursor having an acid residue or an amine residue having a biphenyl structure is preferable. That is, it is preferable that the resin (A) contains a polyimide precursor having a biphenyl structure. Further, for the purpose of improving the elastic modulus, it is preferable that the resin (A) contains a polyimide precursor having a residue of a trivalent or higher amino compound.

In the general formula (6), X represents a tetravalent to 14-valent organic group having two or more carbon atoms. Y each independently represents a divalent to 14-valent organic group having two or more carbon atoms. R ^a and R ^b each independently represent either 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. However, when the value of p, q, r, and s is 0, the functional groups in parentheses each represent a hydrogen atom. Here, in this specification, when it is written as "~", it means that the upper and lower limit numbers are included unless otherwise specified.

In the general formula (6), X is derived from a tetra-, hexa-, octa-, or decacarboxylic acid residue or a residue of a derivative thereof (hereinafter, these are collectively referred to as "acid residue"). Further, by using an acid component corresponding to these acid residues during polymerization, these acid residues can be included in the structural unit. Examples of carboxylic acid compounds 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-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3-dicarboxyphenyl)methane, , 4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid or 3, Aromatic tetracarboxylic acids such as 4,9,10-perylenetetracarboxylic acid or 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-entetracarboxylic acid, bicyclo[2.2.2. ] Aliphatic tetracarboxylic acids such as octanetetracarboxylic acid or adamatanetetracarboxylic acid, and the like. Among these, for the purpose of achieving both high exposure sensitivity and low linear thermal expansion coefficient, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2 , 2',3,3'-biphenyltetracarboxylic acid is preferred. In addition, examples of the acid component having a valence of 6 or higher include the following compounds.

In the above formula, a plurality of R ^c 's represent any of the following structures.

These acids can be used as they are, or as acid anhydrides, acid chlorides, or active esters. Activated ester groups include, but are not limited to, the following structures.

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 t-butyl group, a trifluoromethyl group, a halogen group, a phenoxy group, a nitro group, etc. Not done.

In addition, preferable structures of the acid residue of , a nitro group, a cyano group, a structure substituted with a fluorine atom or a chlorine atom.

However, J is a direct bond, -COO-, -CONH-, -CH ₂ -, -C ₂ H ₄ -, -O-, -C ₃ H ₆ -, -SO ₂ -, -S-, -Si( CH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -O-, -C ₆ H ₄ -, -C ₆ H ₄ -O-C ₆ H ₄ -, -C ₆ H ₄ -C ₃ H ₆ -C ₆ H ₄ - or -C ₆ H ₄ -C ₃ F ₆ -C ₆ H ₄ -.

In addition, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilane diphthalic acid or 1,3-bis(phthalic acid)tetramethyldisiloxane, it is possible to improve adhesion to the substrate, oxygen plasma used for cleaning, UV ozone, etc. Resistance to treatment can be increased. These silicon atom-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% of the total acid components.

In general formula (6), Y represents di-, tri-, tetra-, penta-, hexa-, hepta-, octaamine residue or isocyanate residue (hereinafter collectively referred to as "amine residue"). . Moreover, by using an amine compound or an isocyanate compound having the structure of this amine residue during polymerization, these amine residues can be included in the structural unit.

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- Anthracene diamine, 2,7-diaminofluorene, 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfone Acid-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diamino Diphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 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-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6 -Aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2 -benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6- Bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl) )-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], 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-aminobenzoyl) )-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, bis[N-(3-amino benzoyl)-3-amino-4-hydroxyphenyl] sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl] sulfone, 9,9-bis[N-(3-aminobenzoyl) -3-amino-4-hydroxyphenyl]fluorene, 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-amino benzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis Bisaminophenols such as (4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, some of the hydrogen atoms of these aromatic rings are replaced with alkyl groups having 1 to 10 carbon atoms or fluoroalkyl groups. Examples include, but are not limited to, compounds substituted with groups, halogen atoms, etc., and diamines having the structures shown below.

Among these, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl is preferred. From the viewpoint of low thermal expansion coefficient, 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(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 is preferred. 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'-diamino Diphenylsulfide and 4,4'-diaminobenzophenone are preferred. The other diamine to be copolymerized can be used as it is or as a compound whose amine moiety is isocyanated or trimethylsilylated. Moreover, you may use these two or more types of diamine components in combination.

In addition to the above-mentioned aromatic diamines, aliphatic diamines or diamines having a siloxane structure may be used. Examples of aliphatic diamines include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5- Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane , 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis( aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP- 2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700 (all product names, manufactured by HUNTSMAN Co., Ltd.). Among the above, it is preferable to include an alkylene oxide structure because it can increase flexibility and increase elongation. Further, due to the presence of the ether group in the alkylene oxide structure, it is possible to form a complex or form a hydrogen bond with a metal, thereby achieving high adhesion with the metal. Also, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )-, -N(CH It may include bonds such as (CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, and -NHCONH-.

As the diamine having a siloxane structure, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane are preferable because they can improve adhesiveness with the substrate.

In addition to the above-mentioned diamine components, trivalent or higher valence amine compounds may be mentioned. (A) Because the resin has a residue of a trivalent or higher amine compound, the cured film obtained by curing exhibits a high elastic modulus. Specific examples of trivalent or higher amine compounds include tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenoxy)benzene, and 1,3,5-tris(4-aminophenyl)benzene. , 2,4,4'-triamino diphenyl ether, 3,4,4'-triamino diphenyl ether, 2,4,4'-triamino diphenyl sulfone, 3,4,4'-triamino diphenyl 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 having the following structure Mention may be made of triamines, tetraamines or pentaamines.

In the general formula (6), R ^a and R ^b represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^a is preferably a hydrogen atom, a methyl group, or an ethyl group, since shrinkage after curing becomes small when the resulting photosensitive resin composition is a positive type. R ^a and R ^b are preferably a hydrogen atom from the viewpoint of alkali solubility, and when the resulting photosensitive resin composition is a negative type, an organic group having an ethylenically unsaturated bond is preferable because it improves the sensitivity of exposure.

The method for introducing an organic group having an ethylenically unsaturated bond is, for example, by reacting a tetracarboxylic dianhydride with an alcohol having an ethylenically unsaturated bond to produce a tetracarboxylic acid diester, and then combining this with the structure of Y. It is obtained by an amide polycondensation reaction with an amine compound having the following properties. Moreover, when hexacarboxylic acid trianhydride, octacarboxylic acid tetraanhydride, and decacarboxylic acid pentaanhydride are used, they can be obtained in the same manner.

As a method for producing the above-mentioned tetracarboxylic acid diester, the above-mentioned acid dianhydride and alcohol can be directly reacted in a solvent, but from the viewpoint of reactivity, it is preferable to use a reaction activator. Examples of the reaction activator include tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine, and 1,8-diazabicycloundecene. The amount of the reaction activator added is preferably 10 mol% or more and 300 mol% or less, more preferably 50 mol% or more and 150 mol% or less, based on the acid anhydride group to be reacted. Further, a small amount of a polymerization inhibitor may be used for the purpose of preventing ethylenically unsaturated bond sites from crosslinking during the reaction. Thereby, in the reaction between an alcohol having an ethylenically unsaturated bond with low reactivity and a tetracarboxylic dianhydride, the reaction can be promoted by heating in a range of 120° C. or lower. Examples of the polymerization inhibitor include phenolic compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene. The amount of the polymerization inhibitor added is preferably 0.1 mol% or more and 5 mol% or less of the phenolic hydroxyl group of the polymerization inhibitor relative to the ethylenically unsaturated bond of the alcohol.

Various methods can be used for the above-mentioned amide polycondensation reaction. Examples include a method in which a tetracarboxylic acid diester is converted into an acid chloride and then reacted with a diamine, a method in which a carbodiimide-based dehydration condensation agent is used, and a method in which the tetracarboxylic acid diester is converted into an activated ester and then reacted with a diamine.

Examples of the alcohols having an ethylenically unsaturated bond include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 1-(meth)acryloyloxy-2 -Propyl alcohol, 2-(meth)acrylamidoethyl alcohol, methylol 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-t-butoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexylalkoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexyloxy Alcohols with one ethylenically unsaturated bond and one hydroxyl group, such as propyl (meth)acrylate, 2-(meth)acryloxyethyl-2-hydroxypropyl phthalate, glycerin-1,3-di(meth)acrylate, glycerin- 1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin-1-allyloxy-3-methacrylate, glycerin-1- Ethylenic inorganic compounds such as allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1,3-diylbis(2-methacrylate), and 2-((acryloyloxy)-2-(hydroxymethyl)butyl methacrylate) Examples include alcohols having two or more saturated bonds and one hydroxyl group. Here, "(meth)acrylate" refers to methacrylate or acrylate. The same applies to similar expressions.

When reacting an acid anhydride with an alcohol having an ethylenically unsaturated bond, other alcohols may be used at the same time. Other alcohols can be selected as appropriate for various purposes such as adjusting exposure sensitivity and solubility in organic solvents. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i-pen. Aliphatic alcohols such as tanol, 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 Examples include monoalcohols derived from alkylene oxides such as monoethyl ether and tripropylene glycol monobutyl ether.

Other methods for introducing an organic group having 1 to 20 carbon atoms in R ^a in general formula (6) include, for example, a method in which a polyamic acid is obtained from an acid dianhydride and a diamine, and then esterified by a known method. can be given. Examples of the esterification reaction include a method using trifluoroacetic acid and a compound having a hydroxyl group, and a method involving reacting dimethylformamide dialkyl acetal.

Furthermore, in order to improve the storage stability of the photosensitive resin composition of the present invention and to exhibit various functions, the main chain end of the resin (A) may be capped with a terminal capping agent. Examples of the terminal capping agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Furthermore, monoalcohol can also be used as an end-capping agent in the latter stage of the reaction of the above-mentioned amide polycondensation. In addition, by capping the ends of the resin with a terminal capping agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of the resin in an alkaline solution, exposure sensitivity, The mechanical properties and the like of the resulting cured film can be easily adjusted to a preferred range.

The introduction ratio of the terminal capping agent is preferably 0.1 mol% or more and 60 mol% or less, particularly preferably 5 mol% or more and 50 mol% or less, from the viewpoint of solubility in the developer and mechanical properties of the cured film obtained. A plurality of terminal capping agents may be reacted to introduce a plurality of different terminal groups.

Monoamines used as terminal capping agents include M-600, M-1000, M-2005, M-2070 (all product 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, 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 and the like are preferred. Two or more types of these may be used.

Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 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-carboxybenzenesulfonic acid, and other monocarboxylic acids and their carboxyls. Monoacid chloride compounds in which the group is acid chlorinated, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, Mono-acid chloride compounds in which only one carboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene is acid chloridized, mono-acid chloride compounds and N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3- Active ester compounds obtained by reaction with dicarboximide are preferred. Two or more types of these may be used.

Examples of the monoalcohol used as the terminal capping agent include those exemplified as the alcohols that react with the acid anhydride described above.

Further, the terminal capping agent introduced into the resin (A) used in the present invention can be easily detected by the following method. For example, by dissolving a resin into which an end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are structural units, and measuring this by gas chromatography (GC) or NMR, The terminal capping agent used in the present invention can be easily detected. In addition, by performing GC measurements simultaneously with each component and an external standard whose peaks do not overlap, and comparing the integral value of each peak in the chromatogram with the external standard, it is possible to The ratio can be estimated. Separately, the resin component into which the terminal capping agent has been introduced can be directly measured using a pyrolysis gas chromatograph (PGC), infrared spectrum, ¹ H-NMR spectrum, ¹³ C-NMR spectrum, and two-dimensional NMR spectrum. It is also easily detectable. In this case, the molar ratio of each monomer can be analyzed from the infrared spectrum, ¹ H-NMR spectrum, or two-dimensional NMR integral value.

The polyimide resin (A) can be obtained by partially dehydrating and ring-closing a polyimide precursor by heat treatment or chemical treatment with an acid, a base, or the like. More specifically, heat treatment may be carried out by adding a solvent that is azeotropic with water such as m-xylene, or heat treatment may be carried out by adding a weakly acidic carboxylic acid compound at a low temperature of 100°C or less. . Examples of the ring-closing catalyst used in the above chemical treatment include dehydration condensation agents such as carboxylic acid anhydrides or dicyclohexylcarbodiimide, and bases such as triethylamine. Moreover, it can be obtained by polymerizing an amine compound or a carboxylic acid compound containing an imide group as a monomer as a monomer.

Examples of the polybenzoxazole precursor of the resin (A) include polyhydroxyamide, polyaminoamide, polyamide, or a copolymer with polyamideimide, and polyhydroxyamide is preferred. A polyhydroxyamide having a dicarboxylic acid residue and a bisaminophenol residue can be obtained by reacting a bisaminophenol with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like.

Dicarboxylic acids that serve as monomers for polyhydroxyamide include cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, and tetrafluorosuccinic acid. 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, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid , pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacanedioic acid Aliphatic dicarboxylic acids such as diacid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis Aromatic dicarboxylic acids such as (carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, or triphenyl dicarboxylic acid are mentioned. Further, tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, or biphenyl tricarboxylic acid may be used. Examples of the bisaminophenol include the bisaminophenols listed above among the amine components in which Y is an amine residue.

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

Further, the resin (A) may be a copolymer. Among these, polyimide precursor-polyimide copolymers and polyimide precursor-polybenzoxazole precursor copolymers are preferred. The polyimide precursor-polyimide copolymer is obtained by thermally or chemically imidizing a portion of the polyimide precursor during polymerization. The polyimide precursor-polybenzoxazole precursor copolymer can be obtained by polymerizing the above-mentioned polyhydroxyamide during and/or before and after the reaction to obtain the above-mentioned polyimide precursor. It can also be obtained by polymerizing a polyimide precursor using as a monomer an amine compound or a carboxylic acid compound having a hydroxyamide moiety as a residue in advance.

Examples of the epoxy resin (A) include resins obtained by glycidylating a phenol compound. Phenol compounds include bisphenol A, bisphenol F, bisphenol E, bisphenol AF, bisphenol S, bisphenol fluorene, biphenol, trisphenolmethane, α,α,α'-tris(4-hydroxypheny)-1-ethyl-4- Examples include, but are not limited to, low molecular weight compounds such as isopropylbenzene, and phenolic resins obtained by polycondensation of low molecular weight phenol compounds and aldehyde compounds, including novolac resins. Among these, resins obtained by glycidylating bisphenol A-modified phenol resins and novolac resins are preferred because of their excellent reactivity.

(A) The polysiloxane of the resin is a hydrolyzed/dehydrated condensate of organosilane, and in the present invention, preferably has a hydrophilic group. By having a hydrophilic group in the polysiloxane, developability can be further improved and development residues can be further suppressed. Furthermore, it is more preferable to have a styryl group. By having a styryl group in polysiloxane, hardness and chemical resistance can be further improved.

Examples of the hydrophilic group include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a hydroxyimide group. You may have two or more types of these. Among these, carboxyl groups and carboxylic acid anhydride groups are preferred, and carboxylic acid anhydride groups are more preferred, from the viewpoint of further suppressing development residues and further improving storage stability.

A polysiloxane having a hydrophilic group and a styryl group can be obtained, for example, by hydrolyzing and dehydrating condensation of a plurality of organosilane compounds including an organosilane compound having a hydrophilic group and an organosilane compound having a styryl group. can. Organosilane compounds other than those having a hydrophilic group and a radically polymerizable group may be hydrolyzed and dehydrated together with the organosilane compounds.

As the organosilane compound having a hydrophilic group, an organosilane compound having a carboxylic acid group and/or a carboxylic acid anhydride group is preferable, and an organosilane compound having a carboxylic acid anhydride group is more preferable. For example, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylsuccinic anhydride, Examples include cycilylpropylphthalic anhydride.

A polysiloxane having a styryl group can be obtained, for example, by hydrolyzing and dehydrating condensation of a plurality of organosilane compounds including an organosilane compound having a styryl group. As the organosilane compound having a styryl group, styryltrimethoxysilane and styryltriethoxysilane are preferred, and styryltrimethoxysilane is more preferred. In addition, examples of organosilane compounds other than organosilane compounds having a hydrophilic group and a styryl group include methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, and methyltriisopropoxysilane. , methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltrimethoxysilane Ethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane Methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyl Tri(methoxyethoxy)silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltriethoxysilane, Cidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (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)propyltri Methoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxy Silane, 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-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane , γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropyl Methyldi(methoxyethoxy)silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane , octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane and the like. Two or more types of these may be used.

Polysiloxane can be obtained by hydrolyzing the aforementioned 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.

Various conditions for hydrolysis can be set in accordance with physical properties suitable for the intended use, taking into account the reaction scale, the size and shape of the reaction vessel, etc. Examples of various conditions include acid concentration, reaction temperature, and reaction time.

For 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 acids and their anhydrides, and ion exchange resins can be used. Among these, acidic aqueous solutions containing formic acid, acetic acid and/or phosphoric acid are preferred.

When using an acid catalyst in the hydrolysis reaction, the amount of the acid catalyst added is 0.05 parts by mass per 100 parts by mass of all the alkoxysilane compounds used in the hydrolysis reaction, from the viewpoint of allowing the hydrolysis to proceed more quickly. The amount is preferably at least 1 part by mass, and more preferably at least 0.1 part by mass. On the other hand, from the viewpoint of appropriately adjusting 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, based on 100 parts by mass of the total alkoxysilane compound. Here, the total amount of alkoxysilane compounds refers to an amount that includes all alkoxysilane compounds, their hydrolysates, and their condensates. The hydrolysis reaction can be carried out in a solvent.

The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the photosensitive siloxane resin composition. Among these, from the viewpoint of cured film transmittance and crack resistance, 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-t-butyl ether, γ-butyrolactone, etc. are preferably used.

When a solvent is generated by the hydrolysis reaction, it is also possible to perform the hydrolysis without a solvent. It is also preferable to adjust the concentration to an appropriate level as a photosensitive resin composition by further adding a solvent after the hydrolysis reaction is completed. Furthermore, it is also possible to distill off and remove all or part of the produced alcohol by heating and/or under reduced pressure after hydrolysis, and then add a suitable solvent.

When using a solvent in the hydrolysis reaction, the amount of the solvent added is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, based on 100 parts by mass of the total alkoxysilane compound, from the viewpoint of suppressing gel formation. . On the other hand, the amount of the solvent added is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, based on 100 parts by mass of the total alkoxysilane compound, from the viewpoint of causing the hydrolysis to proceed more quickly.

Moreover, as water used for the hydrolysis reaction, ion exchange water is preferable. The amount of water can be set arbitrarily, but it is preferably 1.0 to 4.0 mol per 1 mol of all the alkoxysilane compounds.

Examples of the method for the dehydration condensation reaction include a method in which a silanol compound solution obtained by a hydrolysis reaction of an organosilane compound is directly heated. The heating temperature is preferably 50° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Further, in order to increase the degree of polymerization of polysiloxane, reheating or addition of a base catalyst may be performed. Further, depending on the purpose, after the hydrolysis, an appropriate amount of the produced alcohol may be distilled off and removed under heating and/or reduced pressure, and then a suitable solvent may be added.

From the viewpoint of storage stability of polysiloxane, it is preferable that the polysiloxane solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed if necessary. As a method for removing the catalyst, water washing, treatment with an ion exchange resin, etc. are preferable from the viewpoint of ease of operation and removability. Water washing is a method in which a polysiloxane solution is diluted with a suitable hydrophobic solvent, washed several times with water, and the resulting organic layer is concentrated using an evaporator or the like. The treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with a suitable ion exchange resin.

The resin (A) in the present invention preferably has a weight average molecular weight of 5,000 or more and 100,000 or less. By setting the weight average molecular weight to 5,000 or more in terms of polystyrene by GPC (gel permeation chromatography), mechanical properties such as elongation, strength at break, and elastic modulus after curing can be improved. On the other hand, by setting the weight average molecular weight to 100,000 or less, developability can be improved. In order to obtain good mechanical properties, it is more preferably 20,000 or more. Furthermore, when the resin (A) contains two or more types of resins, it is sufficient that the weight average molecular weight of at least one of the resins is within the above range.

Moreover, it is preferable that the resin (A) used in the present invention is polymerized using a solvent. The type of polymerization solvent is not particularly limited as long as it can dissolve the acid component, amine component, alcohol, and catalyst that are the raw material monomers. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethyliso Amides of butyric acid amide, methoxy-N,N-dimethylpropionamide, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc. , 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, sulfolane, dimethyl sulfoxide, etc. can be mentioned.

The photosensitive resin composition of the present invention contains (B) a thermal base generator. The thermal base generator (B) is a guanidine derivative and/or a biguanide derivative (hereinafter sometimes abbreviated as "component (B)"). By containing the component (B), the ring-closing reaction of the resin (A) is promoted in the thermosetting step, and polyimide can be obtained even in a low temperature range of 250° C. or lower. Thereby, the mechanical properties, particularly the elongation and strength at break, of the cured film obtained by curing the photosensitive resin composition of the present invention can be improved. Furthermore, the adhesion of the cured film to the metal base can be improved. It is preferable that the thermal base generator (B) contains a guanidine derivative and/or a biguanide derivative having a quaternary boron anion. Component (B) is classified into nonionic and ionic base generators, but ionic base generators are preferred because of their high activity. Further, biguanide derivatives are preferable because the generated base has a higher degree of basicity. Among these, the compound represented by general formula (1) is particularly preferred.

In general formula (1), R ¹ to R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or an aryl group having 7 to 50 carbon atoms. ˜50 arylalkyl groups, Z ⁻ represents a carboxylate or borate anion.

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

The aryl group having 6 to 50 carbon atoms may be monocyclic or fused polycyclic, and specific examples include phenyl, naphthyl, anthracenyl, and phenanthrenyl groups.

The arylalkyl group having 7 to 50 carbon atoms may be monocyclic or fused polycyclic, and specifically includes, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1- Examples include methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group, fluorenyl group, anthracenylmethyl group, phenanthrenylmethyl group, etc. .

In general formula (1), when the organic groups represented by R ¹ to R ⁷ are other than hydrogen atoms, they may be substituted. Substituents for alkyl groups having 1 to 50 carbon atoms include amino groups, nitro groups, epoxy groups, alkoxycarbonyl groups, vinyl groups, (meth)acrylic groups, ethynyl groups, coumarinylcarbonyl groups, anthraquinonyl groups, xanthonyl groups, and A thioxanthonyl group is mentioned. Specific examples of the epoxy group include a glycidyl group and a 2,3-cyclohexyl epoxyethyl group. Specific examples of alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, n-isobutoxycarbonyl group, sec-butoxycarbonyl group, tert- Butoxycarbonyl group, cyclobutoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, neopentyloxycarbonyl group, 2-methylbutoxycarbonyl group, 1 , 2-dimethylpropoxycarbonyl group, 1-ethylpropoxycarbonyl group, cyclopentyloxycarbonyl group, and the like. Specific examples of amino groups include unsubstituted primary amino groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, n-propylamino groups, di-n-propylamino groups, and isopropylamino groups. , diisopropylamino group, n-butylamino group, di-n-butylamino group, isobutylamino group, diisobutylamino group, sec-butylamino group, di-sec-butylamino group, tert-butylamino group, di-tert- Examples include secondary or tertiary amino groups substituted with an alkyl group having 1 to 4 carbon atoms, such as a butylamino group, a cyclobutylamino group, and a dicyclobutylamino group.

Substituents for the aryl group having 6 to 50 carbon atoms or the arylalkyl group having 7 to 50 carbon atoms include alkyl groups, alkoxy groups, coumarinylcarbonyl groups, anthraquinonyl groups, xanthonyl groups, thioxanthonyl groups, halogen atoms and nitro groups. Can be mentioned. The alkyl group may be linear, branched or cyclic, and specific examples include those exemplified above for the alkyl group having 1 to 50 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, cyclobutoxy group, n-pentyloxy group, isopropoxy group, Pentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, 2-methylbutoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, cyclopentyloxy group, n-hexyloxy group , isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, neohexyloxy group, 2-methylpentyloxy group, 1,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethylbutoxy group group, cyclohexyloxy group, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

In the general formula (1), Z ^- represents a carboxylate or borate anion. Carboxylates that give Z ⁻ include aliphatic carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butanoic acid, valeric acid, pivalic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and capric acid, benzoic acid, Examples include carboxylates derived from aromatic carboxylic acid compounds such as 4-benzoylbenzoic acid, salicylic acid, cinnamic acid, and 4-biphenylcarboxylic acid. Furthermore, carboxylates represented by general formula (2) and general formula (3) are mentioned, which are preferable from the viewpoint of storage stability of the photosensitive resin composition of the present invention.

In the general formula (2), R ⁸ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and a C 1 to 50 alkyl group having 6 to 50 carbon atoms. It represents an aryl group, an arylalkyl group having 7 to 50 carbon atoms, or an alkoxy group having 1 to 50 carbon atoms.

In general formula (3), R ¹⁷ to R ²⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and It represents an aryl group, 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.

The alkyl group having 1 to 50 carbon atoms represented by R ⁸ to R ¹⁶ in general formula (2) and R ¹⁷ to R ²⁵ in general formula (3) may be linear, branched or cyclic. Any of these may be used, and specific examples include those exemplified above for the alkyl group having 1 to 50 carbon atoms represented by R ¹ to R ⁷ in general formula (1). The same applies to substituents when substituted. Regarding the aryl group having 6 to 50 carbon atoms and the arylalkyl group having 7 to 15 carbon atoms, those exemplified in the explanation of R ¹ to R ⁷ in general formula (1) can be mentioned. The same applies to Examples of the alkoxy group having 1 to 50 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, cyclobutoxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, 2-methylbutoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, cyclopentyloxy group , n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, neohexyloxy group, 2-methylpentyloxy group, 1,2-dimethylbutoxy group, 2,3-dimethylbutoxy group group, 1-ethylbutoxy group, cyclohexyloxy group, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific structures of the carboxylate represented by general formula (2) or general formula (3) include the following structures.

In the general formula (1), the borate giving Z ^- includes, for example, hydrogen atom- or halogen atom-containing borates such as tetrahydroborate, tetrafluoroborate, tetrachloroborate, and tetrabromoborate, as well as borates in the following general formula (4). The borates shown below are preferred from the viewpoint of storage stability.

In the general formula (4), R ²⁶ to R ²⁹ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, or an alkyl group having 2 to 50 carbon atoms. 50 alkenyl group, alkynyl group having 2 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, arylalkyl group having 7 to 50 carbon atoms, arylalkynyl group having 7 to 50 carbon atoms, furanyl group, thienyl group or pyrrolyl group Indicates the group.

Alkyl group having 1 to 50 carbon atoms, alkoxy group having 1 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, and arylalkyl group having 7 to 50 carbon atoms represented by R ²⁶ to R ²⁹ in general formula (4) Examples of the group include those exemplified in the explanation of R ¹ to R ⁷ in general formula (1), and the same applies to substituents when substituted. Examples of the alkenyl group having 2 to 50 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, isobutenyl group, methacrylic group, Prenyl group, isopentenyl group, cyclopentenyl group, n-hexenyl group, cyclohexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, n-decenyl group, n-undecenyl group, n-dodecenyl group, etc. can be mentioned.

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

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

The organic groups represented by R ²⁶ to R ²⁹ in general formula (4) may be substituted, except for hydrogen atoms and halogen atoms. Specific examples of substituents for 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 shown by R ¹ to R ⁷ in general formula (1), respectively. The organic groups used are the same as those mentioned above. Among these, a halogen atom or a nitro group is preferred, and fluorine is more preferred. The substituent of an alkenyl group having 2 to 50 carbon atoms, an alkynyl group having 2 to 50 carbon atoms, an arylalkynyl group having 7 to 50 carbon atoms, a furanyl group, a thienyl group, and a pyrrolyl group is a substituent of an aryl group having 6 to 50 carbon atoms. The same substituents as those exemplified can be mentioned.

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

In the general formula (5), R ³⁰ is a substituted or unsubstituted 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, or an alkenyl group having 2 to 50 carbon atoms. 50 alkynyl group, 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 furanyl group, a thienyl group, or a pyrrolyl group, R ³¹ to R ³³ represents an aryl group having 6 to 50 carbon atoms.

Further, in general formula (5), the aryl groups R ³¹ to R ³³ are more preferably substituted with an electron-withdrawing group. Examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, a nitro group, and the like, with a fluorine atom being preferred. In addition, it is preferable that one or more of each of an alkyl group having 1 to 50 carbon atoms and an aryl group having 6 to 50 carbon atoms is contained because the solubility in organic solvents is high.

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

Specific examples of component (B) include any combination of the above-mentioned specific examples of biguanide cations and specific examples of carboxylate anions or borate anions. Other specific examples include 1,5,7-triazabicyclo[4.4.0]dec-5-ene acetate, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene phosphoric acid. 5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene benzoate, 1,5,7-triaza 2-(9-oxoxanthen-2-yl)propionic acid Bicyclo[4.4.0]dec-5-ene, guanidium 2-(3-benzoylphenyl)propionate, guanidium acetate, guanidium phosphate, guanidium benzoate, L-arginine, L-arginine acetate, phosphorus Examples include L-arginine acid, L-arginine benzoate, and the like.

Although there is no particular restriction on the content of component (B), it is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A) polyimide precursor. Within this range, pattern processability, solubility, and storage stability can be maintained at appropriate levels while promoting the ring-closing reaction of the polyimide precursor (A). Preferably it is 0.3 parts by mass or more and 7 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less.

The photosensitive resin composition of the present invention contains (C) a photosensitizer. The photosensitive agent (C) contains (c-1) a photoacid generator and/or (c-2) a radical photopolymerization initiator. (C) By containing a photosensitizer, pattern processing becomes possible through exposure and development steps.

The photoacid generator (c-1) is not particularly limited, but among them, a quinonediazide compound can be preferably contained. By containing a quinonediazide compound, a positive pattern can be obtained.

Quinonediazide compounds include those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, those in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and those in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through an ester bond and/or a sulfonamide bond. Examples include those that are combined. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxy polyamino compounds need to be substituted with quinonediazide, it is preferable that on average 40 mol% or more of the entire functional groups be substituted with quinonediazide. By using such a quinonediazide compound, we can create a positive photosensitive resin composition that is sensitive to 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. Obtainable.

Polihidroxy compounds are BIS -Z, BISP -EZ, TEKP -4HBPA, TRISP -HAP, TRISP -PA, TRISP -PA, TRISP -SA, TRISOCR -PA, BISOCHP -Z, BISOCHP -Z, BISP -PZ, BISP -IPZ, BISP -IPZ, BISP -IPZ, BISP -IPZ. SOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industries), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Yokuzai Kogyo), 2,6-dimethoxy Methyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol , BisP-AP (trade name, manufactured by Honshu Kagaku Kogyo), novolak resin, etc., but are not limited to these.

Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Examples include, but are not limited to, sulfides.

Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

Among these, it is more preferable that the quinonediazide compound contains an ester with a phenol compound and a 4-naphthoquinonediazide sulfonyl group. This allows high sensitivity and higher resolution to be obtained with i-line exposure.

(c-1) The content of the photoacid generator is preferably 1 part by mass or more, more preferably 10 parts by mass or more, so that sufficient sensitivity can be obtained after exposure to 100 parts by mass of the (A) polyimide precursor. preferable. Further, the content of the quinonediazide compound is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, so as not to deteriorate the film properties, based on 100 parts by mass of the polyimide precursor (A). By setting the content of the quinonediazide compound within this range, higher sensitivity can be achieved while obtaining the desired film characteristics.

Furthermore, other photoacid generators such as onium salts, diaryl compounds, and iminosulfonium, sensitizers, and the like may be added as necessary. Further, by using an onium salt as the component (B), it can also be made to function as a photocuring agent for epoxy resin. By using an onium salt in the epoxy resin, a negative pattern can be obtained. Examples of onium salts include aromatic iodonium complex salts and aromatic sulfonium complex salts. Among these, specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and trilk. Mylyodonium tetrakis(pentafluorophenyl)borate (manufactured by Rhodia, trade name Rhodosil Photoinitiator 2074), di(4-tert-butyl)iodonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF Japan, trade name CGI BBIC) C1) etc.

Specific examples of aromatic sulfonium complex salts include 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro Co., Ltd., trade name CPI-101A), 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl ) Trifluorophosphate (manufactured by San-Apro Co., Ltd., trade name CPI-210S), 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (manufactured by Asahi Denka Co., Ltd.) , trade name SP-172), a mixture of aromatic sulfonium hexafluoroantimonates containing 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate (manufactured by Dow Chemical Company, trade name UVI-6976), and triphenylsulfonium tris( trifluoromethanesulfonyl) methanide (manufactured by BASF Japan, trade name CGI TPS C1), tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide (manufactured by BASF Japan, trade name GSID26-1), tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate (manufactured by BASF Japan, trade name PAG-290), and the like can be suitably used.

The photoradical polymerization initiator (c-2) is not particularly limited as long as it is a compound that generates radicals upon exposure to light, but examples include alkylphenone compounds, aminobenzophenone compounds, diketone compounds, ketoester compounds, phosphine oxide compounds, and oxime ester compounds. and benzoic acid ester compounds are preferable because they have excellent sensitivity, stability, and ease of synthesis. Among these, alkylphenone compounds and oxime ester compounds are preferred from the viewpoint of sensitivity, and oxime ester compounds are particularly preferred. Further, in the case of a thick film having a processed film thickness of 5 μm or more, a phosphine oxide compound is preferable from the viewpoint of resolution. (c-2) By containing a photoradical polymerization initiator, a negative pattern can be obtained.

Examples of alkylphenone compounds include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- 2-hydroxy -2-Methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy -2-propyl)ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl - phenylketone, α-hydroxyalkylphenone compounds such as benzoin, 4-benzoyl-4-methylphenylketone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy α-Alkoxy such as -2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, 2,3-diethoxyacetophenone, benzyldimethylketal, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Examples include acetophenone compounds such as alkylphenone compounds, acetophenone, and pt-butyldichloroacetophenone. Among these, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4 α-Aminoalkylphenone compounds such as -yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 are preferred because of their high sensitivity.

Examples of phosphine oxide compounds include 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl pentyl)-phosphine oxide.

Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-2-(benzoyloximimino)-1-propanone, 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione- 2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-Phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0- acetyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime), NCI-831, NCI-930 (ADEKA (manufactured by BASF), OXE-03, OXE-04 (all manufactured by BASF), etc. Among these, from the viewpoint of sensitivity, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime), 2-octanedione, 1 -[4-(phenylthio)-2-(O-benzoyloxime)], NCI-831, NCI-930, OXE-03, and OXE-04 are preferred.

Examples of the aminobenzophenone compound include 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone.
Examples of diketone compounds include benzyl.
Examples of the ketoester compound include methyl benzoylformate and ethyl benzoylformate.

Examples of the benzoic acid ester compound include methyl o-benzoylbenzoate, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and ethyl p-diethylaminobenzoate.

Other specific examples of the photoradical polymerization initiator (c-2) include benzophenone, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, Hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl- N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N, N-trimethyl-1-propenaminium chloride monohydrate, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, anthraquinone, 2-t- Butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p- -azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, and the like.

(c-2) The content of the photoradical polymerization initiator is 100 parts by mass of the sum of (A) the resin and (D) a compound containing two or more ethylenically unsaturated bonds, which will be described later. In this case, 0.5 parts by mass or more and 20 parts by mass or less is preferable because sufficient sensitivity can be obtained and the amount of outgassing during thermosetting can be suppressed. Among these, 1.0 parts by mass or more and 10 parts by mass or less is more preferable.

The photosensitive resin composition of the present invention may contain a sensitizer for the purpose of enhancing the function of (c-2) the radical photopolymerization initiator. By containing a sensitizer, it becomes possible to improve the sensitivity and adjust the sensitive wavelength. As a sensitizer, bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, Examples include, but are not limited to, N-phenylmorpholine and derivatives thereof.

In the case of a negative photosensitive resin composition, the photosensitive resin composition of the present invention may contain (D) a compound having two or more ethylenically unsaturated bonds (hereinafter sometimes abbreviated as "component (D)"). good. By containing component (D), the crosslinking density during exposure is improved, so that the exposure sensitivity is further improved. Moreover, the chemical resistance of the cured film is further improved. Furthermore, various functions such as hydrophobicity and elongation can be added by selecting a molecular structure according to the purpose as described below.

Component (D) includes, for example, 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-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate Methacrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, penta Erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate , tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol 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-( Examples include meth)acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene.

If you want to further improve the exposure sensitivity, use pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or tripentaerythritol octaacrylate, which improves adhesion during development by improving hydrophobicity. If desired, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate, or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene is preferable. If it is desired to improve the elongation of the membrane, tetraethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate are preferred.

Examples of other compounds of component (D) include epoxy (meth)acrylate obtained by reacting a polyfunctional epoxy compound and (meth)acrylic acid. Since epoxy (meth)acrylate adds hydrophilicity, it can be used for the purpose of improving alkali developability. Examples of the polyfunctional epoxy compound include the following compounds. These polyfunctional epoxy compounds are preferable because they have excellent heat resistance and chemical resistance.

The molecular weight of component (D) is preferably 5,000 or less, more preferably 2,000 or less. If it is 5000 or less, compatibility with the resin (A) is maintained and occurrence of phenomena such as whitening of the film can be reduced, which is preferable.

The content of component (D) is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the resin (A). Within this range, the effects of improving exposure sensitivity and chemical resistance of the cured film can be easily obtained.

The photosensitive resin composition of the present invention may contain an antioxidant. By containing an antioxidant, it is possible to suppress yellowing of the cured film during the post-process heat treatment and a decrease in mechanical properties such as elongation. Further, it is preferable because it can suppress oxidation of the metal material due to its antirust effect on the metal material.

The antioxidant is preferably a hindered phenol antioxidant or a hindered amine antioxidant. Furthermore, the number of phenol groups or amino groups in one molecule is preferably 2 or more, more preferably 4 or more, since it is easy to obtain an antioxidant effect.

Examples of hindered phenolic antioxidants include, but are not limited to, the following structures.

Hindered phenol antioxidants also have the effect of improving resolution because they suppress the diffusion of radicals. Furthermore, when it can be developed with an alkaline aqueous solution, it acts as a dissolution promoter and also has a residue suppressing effect.

Examples of hindered amine antioxidants include bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl ] Butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1,2,2 , 6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane reaction product, tetrakis(1,2,2,6,6-pentamethyl-4-pyridyl)butane-1,2,3,4- Examples include tetracarboxylate or tetrakis(2,2,6,6-tetramethyl-4-pyridyl)butane-1,2,3,4-tetracarboxylate.

Other antioxidants include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine, and 4-methoxyphenol. The amount of the antioxidant added is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.3 parts by mass or more and 5.0 parts by mass or less, per 100 parts by mass of the (A) resin. preferable. Within this range, developability and the effect of suppressing discoloration due to heat treatment can be maintained appropriately.

The photosensitive resin composition of the present invention may contain a nitrogen atom-containing heterocyclic compound. By having a heterocyclic compound containing a nitrogen atom, high adhesion can be obtained on the base of metals that are easily oxidized such as copper, aluminum, and silver. Although the mechanism is not clear, it is presumed that the nitrogen atom interacts with the metal surface due to its metal coordination ability, and the bulk of the heterocycle stabilizes this interaction.

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

More specifically, the heterocyclic compound containing a nitrogen atom 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-t-butyl-5-phenyl-1H-triazole, 5 -Hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)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-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5- Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-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-tri(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-triazin-2-yl)-5-hydroxyphenyl, tris((meth)acryloyloxyethyl)isocyanurate, tris(glycidyloxyethyl)isocyanurate, etc. .

Among these, 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 and the like are preferred.

The amount of the nitrogen atom-containing heterocyclic compound added is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, and 0.05 parts by mass or more and 3.0 parts by mass, based on 100 parts by mass of the resin (A). Part or less is more preferable. Within this range, developability and the stabilizing effect of the base metal can be maintained appropriately.

The photosensitive resin composition of the present invention may contain a solvent. As a solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - Polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate Examples include 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 types of these may be contained.

The content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition with respect to 100 parts by mass of the resin (A), and 1,500 parts by mass in order to form a coating film with a thickness of 1 μm or more. It is preferable to contain less than 1 part.

The photosensitive resin composition of the present invention may optionally contain surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl It may contain ketones such as isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.

Furthermore, in order to improve the adhesion to the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent as a silicon component within a range that does not impair storage stability. Silane coupling agents include trimethoxyaminopropylsilane, trimethoxycyclohexylepoxyethylsilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, trimethoxyglycidyloxypropylsilane, tris(trimethoxysilylpropyl)isocyanurate, triethoxyamino Propylsilane, triethoxycyclohexylepoxyethylsilane, triethoxyvinylsilane, triethoxythiolpropylsilane, triethoxyglycidyloxypropylsilane, tris(triethoxysilylpropyl)isocyanurate and trimethoxyaminopropylsilane or triethoxyaminopropylsilane Examples include reactants with acid anhydrides. The reactant can be used in an amic acid state or an imidized state. The acid anhydrides to be reacted include succinic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4 '-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxydiphthalic acid Examples include dianhydrides. The preferable content of the silane coupling agent is 0.01 to 10 parts by weight based on 100 parts by weight of the resin (A).

Next, the shape of the photosensitive resin composition of the present invention will be explained.

The shape of the photosensitive resin composition of the present invention is not limited as long as it contains the resin (A), the photopolymerization initiator (B), and the component (C), such as a paste or a sheet. It may be.

Furthermore, the photosensitive sheet of the present invention refers to a completely photosensitive sheet obtained by coating the photosensitive resin composition of the present invention on a support and drying it at a temperature and time within a range that allows the solvent to volatilize. An uncured sheet-like material that is soluble in organic solvents or alkaline aqueous solutions.

The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the photosensitive resin composition may be subjected to surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like in order to improve adhesion and releasability. Further, the thickness of the support is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 μm. Furthermore, in order to protect the film surface of the photosensitive composition obtained by coating, a protective film may be provided on the film surface. Thereby, the surface of the photosensitive resin composition can be protected from pollutants such as dust and dirt in the atmosphere.

Methods for applying the photosensitive resin composition to the support include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, and comma roll. Examples of methods include coater, gravure coater, screen coater, and slit die coater. Although the coating film thickness varies depending on the coating method, solid content concentration of the composition, viscosity, etc., the film thickness after drying is usually 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity. preferable.

For drying, an oven, hot plate, infrared rays, etc. can be used. The drying temperature and drying time may be within a range that allows the solvent to volatilize, and it is preferable to set the drying temperature and time appropriately within a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, it is preferable to conduct the heating at a temperature ranging from 40°C to 150°C for 1 minute to several tens of minutes. Further, the temperature may be increased stepwise by combining these temperatures, for example, heat treatment may be performed at 80° C. and 90° C. for 2 minutes each.

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

The photosensitive resin composition of the present invention is applied to a substrate, or the photosensitive sheet is laminated onto a substrate. As the substrate, a metal copper plated substrate, a silicon wafer, and as the material, ceramics, gallium arsenide, etc. are used, but the material is not limited to these. Application methods include spin coating using a spinner, spray coating, and roll coating. Although the thickness of the coating film varies depending on the coating method, solid content concentration of the composition, viscosity, etc., the coating is usually done so that the film thickness after drying is 0.1 to 150 μm.

In order to improve the adhesion between the substrate and the photosensitive resin composition, the substrate can also be pretreated with the above-mentioned silane coupling agent. For example, a solution in which 0.5 to 20% by mass of a silane coupling agent is 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. Create. Next, the surface of the substrate is treated with the prepared solution by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, heat treatment is then performed at 50° C. to 300° C. to advance the reaction between the substrate and the silane coupling agent.

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 carried out using an oven, hot plate, infrared rays, etc. at a temperature in the range of 50° C. to 150° C. for 1 minute to several hours. In addition, in the case of a photosensitive sheet, it is not necessary to go through a drying process.

Next, this photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. .

Next, the exposed photosensitive resin film may be subjected to a post-exposure bake (PEB) process, if necessary. The PEB process is preferably carried out at a temperature of 50° C. to 150° C. for 1 minute to several hours using an oven, hot plate, infrared rays, or the like.

To form a resin pattern, after exposure, a developer is used to remove the unexposed areas in the case of a negative type, and the exposed areas in the case of a positive type. The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone and the like are preferred. Preferred examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Moreover, two or more types of each solvent, for example, several types can be used in combination.

On the other hand, in the case of a photosensitive resin composition that dissolves in an alkaline aqueous solution, the developer used for development is one that dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved. . Alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Examples include aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be contained alone or in combination. good. After development, it is preferable to perform rinsing treatment with an organic solvent or water. When using an organic solvent, in addition to the above developer, examples include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. When water is used, the rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, and propylene glycol monomethyl ether acetate to the water.

After development, a temperature of 150° C. to 350° C. is applied to advance a thermal crosslinking reaction and cure the film. This heat treatment is carried out either by selecting a certain temperature and increasing the temperature stepwise, or by selecting a certain temperature range and increasing the temperature continuously for 5 minutes to 5 hours. For example, heat treatment is performed at 130° C. and 200° C. for 30 minutes each. The lower limit of the curing conditions in the present invention is preferably 170° C. or higher, and more preferably 180° C. or higher to allow curing to proceed sufficiently. Further, there is no particular restriction on the upper limit of the curing conditions, but from the viewpoint of suppressing film shrinkage and stress, a temperature of 280° C. or lower is preferable. Moreover, since the present invention provides a cured film that is particularly excellent in low-temperature curability, the temperature is more preferably 250°C or lower, and even more preferably 230°C or lower.

A cured film formed from 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 is suitable for applications such as passivation films for semiconductors, surface protection films for semiconductor elements, interlayer insulating films, interlayer insulating films in multilayer wiring for high-density packaging of 2 to 10 layers, and insulating layers for organic electroluminescent devices. However, the present invention is not limited thereto, and various structures can be adopted. In addition, the substrate surface on which the cured film is formed can be selected as appropriate depending on the application and process, but examples include silicon, ceramics, metal, epoxy resin, etc. Even if the substrate surface is made of two or more of these materials, good.

Next, an example of application to a semiconductor device having bumps using a cured film obtained by curing the photosensitive resin composition of the present invention will be described with reference to the drawings. FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having bumps according to the present invention. As shown in FIG. 1, a passivation film 3 is formed on a silicon wafer 1 on an input/output aluminum (hereinafter abbreviated as Al) pad 2, and a via hole is formed in the passivation film 3. On this, an insulating film 4 is formed as a pattern of a cured film obtained by curing the photosensitive resin composition of the present invention, and further a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2. Metal wiring (Al, Cu, etc.) 6 is formed by electrolytic plating or the like. The metal film 5 is etched around the solder bump 10 to provide insulation between each pad. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. A cured film obtained by curing the photosensitive resin composition of the insulating film 7 can be subjected to thick film processing in the scribe line 9 .

In addition, the cured film of the present invention has excellent elongation at break and strength at break when polyimide resin is used, so stress from the sealing resin can be alleviated even during mounting, so the low-k layer It is possible to prevent damage to semiconductor devices and provide highly reliable semiconductor devices.

Next, a detailed method for manufacturing the semiconductor device will be described in FIG. As shown in 2a of FIG. 2, an input/output Al pad 2 and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed as a pattern of a cured film made of the photosensitive resin composition of the present invention. . Subsequently, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. 2, a metal wiring 6 is formed by plating. Form a film. Next, as shown in 2d' of FIG. 2, the photosensitive resin composition of the present invention before curing is applied, and a photolithography process is performed to form the insulating film 7 in a pattern as shown in 2d of FIG. At this time, the photosensitive resin composition before curing of the insulating film 7 is subjected to thick film processing in the scribe line 9. If the target thickness cannot be achieved with one application, multiple applications may be applied. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

Next, as shown in 2e and 2f of FIG. 2, barrier metal 8 and solder bumps 10 are formed. Then, it is diced along the last scribe line 9 and cut into chips. If a pattern is not formed in the insulating film 7 at the scribe line 9 or if a residue remains, cracks etc. will occur during dicing, which will affect reliability evaluation of the chip. Therefore, the ability to provide pattern processing that is excellent in thick film processing as in the present invention is highly desirable in order to obtain high reliability of semiconductor devices.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Note that Examples 1 to 9 and 11 to 36 shall be read as Reference Examples 1 to 35. First, evaluation methods in each example and comparative example will be explained. For the evaluation, an uncured photosensitive resin composition (hereinafter referred to as varnish) that had been filtered in advance through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore diameter of 1 μm was used.

(1) Molecular Weight Measurement (A) The weight average molecular weight (Mw) of the resin was confirmed using a GPC (gel permeation chromatography) device Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.). The developing solvent was measured as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the weight average molecular weight (Mw) and dispersity (PDI=Mw/Mn) were calculated in terms of polystyrene.

(2) Pattern processability (2)-1 Sensitivity A
The varnish using polyimide resin and epoxy resin obtained in each Example and Comparative Example was spin-coated onto a silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.), and then a hot plate (Dainippon Co., Ltd.) was applied. A prebaked film having a thickness of 11 μm was prepared by prebaking at 120° C. for 3 minutes using a film (SCW-636 manufactured by Screen Seizo Co., Ltd.). Sensitivity was adjusted on the obtained pre-baked film using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source (mixed line of g-line, h-line, and i-line). Gray scale mask for measurement (2 to 50 μm, 1:1 line & space pattern. 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, respectively) It has areas with transmittances of 22%, 25%, 30%, 35%, 40%, 50% and 60%). Thereafter, if the varnish was negative type, it was exposed and baked at 120° C. for 1 minute, and developed using a coating and developing device MARK-7. If the polymer was not soluble in the alkaline aqueous solution, shower development was performed for 2 minutes using cyclopentanone as a developer, followed by rinsing for 30 seconds with propylene glycol monomethyl ether acetate. When the polymer is dissolved in an alkaline aqueous solution, a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution (trade name: "ELM-D", manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used as the developer. Paddle development was carried out for 90 seconds, followed by a 30 second rinse with water.

After development, the film thickness was measured, and the minimum exposure amount at which the remaining film rate in the exposed area exceeded 90% was defined as the sensitivity. The exposure amount was measured with an I-ray luminometer.
The film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. with a refractive index of 1.629. The same applies to the film thickness described below.

(2)-2 Sensitivity B
Using a spin coater, a varnish using the polysiloxane obtained in each example and comparative example was spin coated onto a 10 cm square alkali-free glass substrate, and then coated using a hot plate at a temperature of 90°C for 2 minutes. A prebaked film having a thickness of 2 μm was prepared by prebaking.

The prepared pre-baked film was coated with PLA-501F using an ultra-high pressure mercury lamp as a light source (mixed line of G-line, H-line, and I-line), and a gray scale mask for sensitivity measurement (2-50 μm, 1:1 line). & space pattern: 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50% respectively and has an area with a transmittance of 60%). Then, using an automatic developing device ("AD-2000 (product name)" manufactured by Takizawa Sangyo Co., Ltd.), shower with 0.045% by mass potassium hydroxide aqueous solution or 2.38% by mass TMAH for 100 seconds. Developed and then rinsed with water for 30 seconds. After development, the film thickness was measured, and the minimum exposure amount at which the remaining film rate in the exposed area exceeded 90% was defined as the sensitivity. The exposure amount was measured with an I-ray luminometer.
The film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. with a refractive index of 1.550. The same applies to the film thickness described below.

(2)-3 Developability A
(2) The minimum pattern size after development at the exposure amount at sensitivity A defined in -1 was measured.

(2)-4 Developability B
(2) The minimum pattern size after development at the exposure amount at sensitivity B defined in -2 was measured.

(3) Evaluation of chemical resistance (3)-1 Chemical resistance evaluation A
The varnish using polyimide resin and epoxy resin obtained in each Example and Comparative Example was applied onto a silicon wafer by pre-baking at 120°C for 3 minutes, and then coated with a developing device MARK so that the film thickness was 10 μm. -7 using a spin coating method and prebaking, then if it is a negative type, expose the entire surface to 300 mJ/ ^cm2 using PLA-501F, or if it is a positive type, leave it as it is in an inert oven CLH-21CD- Using S, the temperature was raised to 180° C. at a rate of 3.5° C. per minute at an oxygen concentration of 20 ppm or less under a nitrogen stream, and heat treatment was performed at each temperature for 1 hour. When the temperature drops to below 50°C, the silicon wafer is taken out and the cured film is immersed in an organic chemical solution (dimethyl sulfoxide: 25% by mass TMAH aqueous solution = 92:2) at 40°C for 10 minutes to prevent pattern peeling and film thickness. Changes (indicating swelling or elution volume) were observed. The results are 4: No pattern peeling and film thickness change of 5% or less, 3: No pattern peeling and film thickness change of more than 5% but 10% or less, 10: No pattern peeling and film thickness change of 5% or less. % but not more than 30% was evaluated as 2, and cases where the pattern peeled off and no film remained or the film thickness change exceeded 30% were evaluated as 1.
The less the pattern peels off and the smaller the change in film thickness, the better the chemical resistance.

(3)-2 Chemical resistance evaluation B
A varnish using the polysiloxane obtained in each Example and Comparative Example was spin-coated using a spin coater onto a glass substrate (hereinafter referred to as "ITO substrate") whose surface had been sputtered with ITO, and then a hot plate ( Using SCW-636 (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.), prebaking was performed at 100° C. for 2 minutes to produce a film with a thickness of 2.0 μm.

The produced film was exposed to 300 mJ/cm ² using PLA-501F, and cured in air at 170°C for 1 hour using an oven (product name IHPS-222, manufactured by ESPEC Co., Ltd.) to produce a cured film. did.

The resulting cured film was immersed in a resist stripping solution, N300, at 50° C. for 3 minutes, and peeling of the pattern and change in film thickness (indicating swelling or elution amount) were observed. The results were evaluated in the same manner as in (3)-1 Chemical resistance evaluation A above.

(4) Measurement of elongation at break and strength at break The varnish using polyimide and epoxy resin obtained in each example and comparative example was prebaked at 120°C for 3 minutes on a 6-inch silicon wafer. After coating and pre-baking using a spin coat method using a coating and developing device ACT-8 so that the film thickness is 11 μm, in the case of a negative type, the entire surface is exposed to light of 300 mJ/cm ² using PLA, and in the case of a positive type. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was increased to 180°C at a rate of 3.5°C/min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at each temperature for 1 hour. I did it. When the temperature reached 50° C. or lower, the silicon wafer was taken out and immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. This film was cut into strips with a width of 1.5 cm and a length of 9 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was stretched at a room temperature of 23.0°C and a humidity of 45.0% RH. The elongation at break (%) and strength at break (MPa) were measured by pulling at 50 mm/min (chuck interval = 2 cm). The measurement was performed on 10 strips per sample, and the average value of the top 5 highest numerical values was determined from the results (significant figures = 2 digits). This evaluation was carried out as an evaluation of the mechanical properties of polyimide and epoxy resin.

(5) Copper board adhesion evaluation (5)-1 Copper board adhesion evaluation A
Adhesion to metallic copper was evaluated using the following method.

First, varnish is applied by spin coating onto a metallic copper plated substrate with a thickness of about 3 μm, and then baked for 3 minutes at 120°C using a hot plate (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a prebaked film with a thickness of 8 μm was produced. In the case of a negative type, the entire surface is exposed to 300 mJ/ ^cm2 using PLA, and in the case of a positive type, the film is exposed to oxygen concentration using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.). The temperature was raised to 230° C. at a rate of 3.5° C./min at 20 ppm or less, and heat treatment was performed at 230° C. for 1 hour. When the temperature dropped to 50° C. or less, the substrate was taken out, divided into two parts, and cuts were made in the cured film of each substrate in a grid pattern of 10 rows and 10 columns at 2 mm intervals using a single blade. Using one of the sample substrates, the adhesion characteristics between the metal material and the cured resin film were evaluated based on how many squares out of 100 squares were peeled off using "cellotape" (registered trademark). The other sample substrate was subjected to PCT treatment for 400 hours at 121°C and 2 atm pressure using a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai Spec Co., Ltd.). After that, the above peeling test was performed. For any of the substrates, 0 pieces were peeled off in the peel test, 5 pieces were peeled off, 1 piece or more and less than 10 pieces were rated 4, 10 pieces or more and less than 30 pieces were rated 3, 30 pieces or more and less than 50 pieces were rated 2, and 50 pieces or more was rated 1.

The smaller the number of peeled pieces, the better the adhesion.

(5)-2 Copper substrate adhesion evaluation B
A cured film having a thickness of 2.0 μm was formed on a copper substrate in the same manner as in the method described in (3)-2 above. The obtained substrate was divided into two parts, and incisions in a grid pattern of 10 rows and 10 columns at 2 mm intervals were made in the cured film of each board using a single blade. Using one of the sample substrates, the adhesion characteristics between the metal material and the cured resin film were evaluated based on how many squares out of 100 squares were peeled off using "cellotape" (registered trademark). The other sample substrate was subjected to PCT treatment for 25 hours at 85°C and 85% using a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai Spec Co., Ltd.). , the peel test described above was conducted. The adhesion was determined in the same manner as in (5)-1 Copper substrate adhesion evaluation A above.

(6) Measurement of imidization rate The imidization rate (%) of the cured film can be easily determined by the following method. A cured film was produced on the silicon wafer by performing the same procedure as in (4) up to the heat treatment. Next, we measured the infrared absorption spectrum of the prepared cured film (using the silicon wafer as the baseline) and confirmed the presence of absorption peaks of the imide structure (around 1780 cm ^-1 and around 1377 cm ^-1 ) caused by polyimide, Find the peak intensity (X) near 1377 cm ^-1 . Next, the cured film is heat treated at 350° C. for 1 hour, the infrared absorption spectrum is measured, and the peak intensity (Y) around 1377 cm ⁻¹ is determined. These peak intensity ratios correspond to the content of imide groups in the polymer before heat treatment, that is, the imidization rate (imidization rate=X/Y×100(%)).

(7) Storage stability of varnish The viscosity of the varnish after preparation and after being left for two weeks at 23°C was measured, and the rate of change in viscosity before and after being left was calculated.

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

(8) Hardness A cured film with a thickness of 2.0 μm obtained in the same manner as the method described in (3)-2 above was formed on an ITO substrate. The pencil hardness of the obtained cured film was measured in accordance with JIS "K5600-5-4 (establishment date = April 20, 1999)". This evaluation was carried out as an evaluation of the mechanical properties of polysiloxane.

(9) Coefficient of linear thermal expansion (CTE)
A self-supporting film of the cured film was prepared using the same procedure as in (4), and this film was cut out with a single blade to a size of 3.0 cm x 0.5 cm, and a differential scanning calorimeter (Seiko Instruments, TMA/SS6100) was used. The temperature was raised from 25° C. to 400° C. at a rate of 10° C./min under nitrogen flow at 80 mL/min. The coefficient of linear expansion from 50° C. to 150° C. was calculated as CTE (10 ⁻⁶ /K).

[Synthesis Example 1 Synthesis of polyimide precursor (P-1)]
31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 500 ml separable flask, and 26.03 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA) and γ 76 ml of butyrolactone was added thereto, and 16.22 g (0.21 mol) of pyridine was added at room temperature with stirring to obtain a reaction mixture. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 41.27 g (0.2 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 140 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by 4,4'- While stirring, 18.62 g (0.093 mol) of diaminodiphenyl ether (DAE) was added in 5 portions over 20 minutes. After further stirring at room temperature for 2 hours, 6 ml of ethyl alcohol (EtOH) was added and stirred for 1 hour, and then 65 mL of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 800 ml of EtOH to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 6 L of water to precipitate the polymer, and this precipitate was collected by filtration, washed three times with water, and then vacuum dried to obtain a powdered polyimide precursor (P-1). I got it. When the molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 31,000, and the PDI was 2.6. The polyimide precursor (P-1) is insoluble in an alkaline aqueous solution, and a photosensitive resin composition using it is developed with 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.

[Synthesis Example 2 Synthesis of polyimide precursor (P-2)]
Under a stream of dry nitrogen, 62.04 g (0.2 mol) of ODPA was dissolved in 1000 g of NMP. To this, 96.72 g (0.16 mol) of diamine (HA) with 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. The mixture was 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 an end-capping agent was added together with 30 g of NMP, and the mixture was reacted at 50° C. for 2 hours. Thereafter, a solution of 47.66 g (0.4 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then poured into 1 L of water to obtain a precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 20 hours to obtain a powder of polyimide precursor resin (P-2). When the molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 25,000, and the PDI was 2.3. The polyimide precursor (P-2) is soluble in an alkaline aqueous solution, and a photosensitive resin composition using it is developed with a 2.38% by mass TMAH aqueous solution.

[Synthesis Example 3 Synthesis of polyimide precursor (P-3)]
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 polyimide precursor (P-3) had an Mw of 34,000 and a PDI of 2.5. The polyimide precursor (P-3) is developed with cyclopentanone.

[Synthesis Example 4 Synthesis of polyimide precursor (P-4)]
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 in place of 18.62 g of DAE. A polyimide precursor (P-4) was obtained in the same manner as above. The polyimide precursor (P-4) had an Mw of 27,000 and a PDI of 2.9. The polyimide precursor (P-4) is developed with cyclopentanone.

[Synthesis Example 5 Synthesis of polysiloxane (P-5) solution]
In 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), and 3-trimethoxysilyl. 11.80 g (0.045 mol) of propylsuccinic anhydride (Suc), 0.173 g of TBC, and 74.58 g of PGME were charged, and while stirring at room temperature, 17.01 g of water was mixed with 0.348 g of phosphoric acid (the monomer charged). A phosphoric acid aqueous solution containing 0.50% by mass) was added over 30 minutes. Thereafter, the three-necked flask was immersed in a 70°C oil bath and 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 temperature rise, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Note that nitrogen was flowed at 0.05 liters/minute during the temperature rise and heating and stirring. During the reaction, a total of 36.90 g of byproducts methanol and water were distilled out. PGME was added to the obtained polysiloxane solution so that the solid content concentration was 40% by mass to obtain a polysiloxane (P-5) solution.

[Synthesis Example 6 Synthesis of polysiloxane (P-6) solution]
In a 500 ml three-neck flask, 44.86 g (0.200 mol) of p-styryltrimethoxysilane (St), 39.66 g (0.200 mol) of phenyltrimethoxysilane (Ph), and 6 methyltrimethoxysilane (Me). .81 g (0.050 mol), 13.12 g (0.050 mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.522 g of TBC, and 74.58 g of PGME were charged, and while stirring at room temperature, A phosphoric acid aqueous solution containing 0.448 g of phosphoric acid (0.50% by mass based on the monomers charged) dissolved in 27.90 g of water was added over 30 minutes. Thereafter, the three-necked flask was immersed in a 70°C oil bath and 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 temperature rise, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. Note that nitrogen was flowed at 0.05 liters/minute during the temperature rise and heating and stirring. During the reaction, a total of 58.90 g of byproducts methanol and water were distilled out. PGME was added to the obtained polysiloxane solution so that the solid content concentration was 40% by mass to obtain a polysiloxane (P-6) solution.

The base generators used in Examples and Comparative Examples are shown below.

B-I: 1,5,7-triazabicyclo[4.4.0]dec-5-ene 2-(9-oxoxanthen-2-yl)propionic acid

B-II: Guanidium 2-(3-benzoylphenyl)propionate

B-III: Compound with the following structure

B-IV: Compound with the following structure

BV: Compound with the following structure

B-VI: Compound with the following structure

B-VII: Compound with the following structure

B-VIII: Compound with the following structure

B-IX: Compound with the following structure

B-X: Nt-butoxycarbonyldimethylpiperidine

[Example 1]
Under a yellow light, 10.00 g of polyimide precursor (P-1), 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] ("Irgacure OXE-01 ( (Product name) manufactured by BASF) 0.50 g, B-I 0.30 g, NK Ester 4G (Product name) (manufactured by Shin-Nakamura Chemical Co., Ltd., chemical name: Tetraethylene glycol dimethacrylate) 2.00 g, N-phenyl 0.2 g of diethanolamine and 0.30 g of 3-trimethoxysilyl phthalamic acid were dissolved in 15.15 g of N-methylpyrrolidone (NMP) and 3.81 g of ethyl lactate (EL), and acrylic surfactant "Polyflow" 77 (trade name)" (manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred to obtain a varnish. The characteristics of the obtained varnish were evaluated according to the above evaluation method: pattern processability (sensitivity A, developability A), chemical resistance A, elongation at break, strength at break, thermal linear expansion coefficient, copper substrate adhesion evaluation A, imide The conversion rate and storage stability were measured.
[Example 2]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-II.
[Example 3]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-III.
[Example 4]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-IV.
[Example 5]
The same procedure as in Example 1 was carried out except that BI was replaced with BV.
[Example 6]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-VI.

[Example 7]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-VII.
[Example 8]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-VIII.
[Example 9]
The same procedure as in Example 1 was carried out except that BI was replaced with B-IX.
[Example 10]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-3.
[Example 11]
The same procedure as in Example 3 was carried out except that P-1 was replaced with P-4.

[Example 12]
The same procedure as in Example 3 was carried out except that the amount of B-III added was 0.01 g.
[Example 13]
The same procedure as in Example 3 was carried out except that the amount of B-III added was 0.03 g.
[Example 14]
The same procedure as in Example 3 was carried out except that the amount of B-III added was 0.7 g.
[Example 15]
The same procedure as in Example 3 was carried out except that the amount of B-III added was 1.0 g.
[Example 16]
The same procedure as in Example 3 was carried out except that the amount of B-III added was 2.0 g.
[Example 17]
Under a yellow light, 10.00 g of polyimide precursor (P-1), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- 1-butanone (“Irgacure 379 (trade name)” manufactured by BASF) 0.80 g, diethylthioxanthone 0.2 g, B-III 0.30 g, 4G 2.00 g, N-phenyldiethanolamine 0.2 g, 3-trimethoxysilyl phthalamide 0.30 g of acid was 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 and stirred to obtain a varnish. The characteristics of the obtained varnish were evaluated according to the above evaluation method: pattern processability (sensitivity A, developability A), chemical resistance A, elongation at break, strength at break, thermal linear expansion coefficient, copper substrate adhesion evaluation A, imide The conversion rate and storage stability were measured.

[Example 18]
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).
[Example 19]
Irgacure 379 was converted into 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (“Irgacure 127 (trade name)”) The same procedure as in Example 17 was carried out except that the material was changed to (manufactured by BASF).
[Example 20]
The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with ethyl p-dimethylaminobenzoate.
[Example 21]
The same procedure as in Example 17 was carried out except that Irgacure 379 was replaced with 4-phenylbenzophenone.
[Example 22]
Instead of the polyimide precursor (P-1), a solid polyfunctional aromatic epoxy resin (YDCN-700-10 (trade name), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), which is a cresol novolak type polyfunctional epoxy resin, was used, and The same procedure as in Example 1 was carried out except that 2 g of pentaerythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku) was added. However, only the imidization rate was not measured.

[Example 23]
Under yellow light, 10.00 g of polyimide precursor (P-2), 2.0 g of TP5-280M (manufactured by Toyo Gosei; 5-naphthoquinonediazide sulfonic acid ester compound of TrisP-PA (manufactured by Honshu Chemical)), B- 0.2 g of I was dissolved in 14.5 g of NMP, 0.10 g of a 1 wt% NMP solution of Polyflow 77 was added, and the mixture was stirred to obtain a varnish. The properties of the obtained varnish were measured by the above evaluation method.
[Example 24]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-II.
[Example 25]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-III.
[Example 26]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-IV.
[Example 27]
The same procedure as in Example 23 was carried out except that BI was replaced with BV.
[Example 28]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-VI.
[Example 29]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-VII.
[Example 30]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-VIII.
[Example 31]
The same procedure as in Example 23 was carried out except that B-IX was replaced with B-I.
[Example 32]
The same procedure as in Example 25 was carried out except that the amount of B-III added was 0.01 g.
[Example 33]
The same procedure as in Example 25 was carried out except that the amount of B-III added was 0.03 g.
[Example 34]
The same procedure as in Example 25 was carried out except that the amount of B-III added was 0.7 g.
[Example 35]
The same procedure as in Example 25 was carried out except that the amount of B-III added was 1.0 g.
[Example 36]
The same procedure as in Example 25 was carried out except that the amount of B-III added was 1.5 g.

[Example 37]
Under yellow light, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (“Irgacure” (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Ltd.) 0.080 g and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” (registered trademark)-819 (trade name), BASF Japan Co., Ltd.) 0.160 g, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irganox” (registered trademark)-245( 0.200 g of PGME 10% by mass solution (trade name), manufactured by BASF Japan Co., Ltd., 0.800 g of pentaerythritol acrylate (“Light Acrylate” (registered trademark) PE-3A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) , 0.16 g of B-I, 0.120 g of 3-methacryloxypropyltrimethoxysila (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, 0.020 g (equivalent to a concentration of 100 ppm) of a 10% by mass diluted solution of silicone surfactant (trade name "BYK" (registered trademark)-333, manufactured by BYK Chemie Japan Co., Ltd.) in PGME was added and stirred. Thereafter, 6.645 g of polysiloxane (P-5) solution was used as polysiloxane (A), and then filtered through a 0.45 μm filter to obtain a polysiloxane-containing varnish. The obtained varnish was evaluated for sensitivity B, developability B, chemical resistance B, hardness, copper substrate adhesion B, and storage stability as described above.
[Example 38]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-II.
[Example 39]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-III.

[Example 40]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-IV.
[Example 41]
The same procedure as Example 37 was carried out except that BI was replaced with BV.
[Example 42]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-VI.
[Example 43]
The same procedure as in Example 37 was conducted except that B-VII was used instead of B-I.
[Example 44]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-VIII.
[Example 45]
The same procedure as in Example 37 was carried out except that BI was replaced with B-IX.

[Example 46]
Under yellow light, 0.240 g of TP5-280M (manufactured by Toyo Gosei; 5-naphthoquinonediazide sulfonic acid ester compound of TrisP-PA (manufactured by Honshu Chemical)), 0.160 g of B-I, 3-methacryloxypropyltrimethoxysilane. (KBM-503 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) 0.120 g and a silicone surfactant (trade name "BYK" (registered trademark)) dissolved in a mixed solvent of 7.565 g of PGME and 3.200 g of PGMEA. 0.020 g (equivalent to a concentration of 100 ppm) of a 10% by mass diluted solution of PGME of PGME-333 (manufactured by BIC Chemie Japan Co., Ltd.) was added and stirred. Thereafter, 8.695 g of polysiloxane (P-6) solution was used as polysiloxane (A), and then filtered through a 0.45 μm filter to obtain a varnish. The obtained varnish was evaluated for sensitivity B, developability B, chemical resistance B, hardness, copper substrate adhesion B, and storage stability as described above.
[Example 47]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-II.
[Example 48]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-III.
[Example 49]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-IV.
[Example 50]
The same procedure as in Example 46 was carried out except that BI was replaced with BV.
[Example 51]
The same procedure as Example 46 was carried out except that B-I was replaced with B-VI.
[Example 52]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-VII.
[Example 53]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-VIII.
[Example 54]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-IX.

[Comparative example 1]
The same procedure as in Example 1 was carried out except that B-I was replaced with B-X.
[Comparative example 2]
The same procedure as in Example 3 was carried out except that OXE-01 was not added.
[Comparative example 3]
The same procedure as in Example 1 was carried out except that BI was not added.
[Comparative example 4]
The same procedure as in Example 23 was carried out except that B-I was replaced with B-X.
[Comparative example 5]
The same procedure as in Example 25 was carried out except that TP5-280M was not added.
[Comparative example 6]
The same procedure as Example 23 was carried out except that BI was not added.
[Comparative Example 7]
The same procedure as Example 22 was carried out except that B-III was not added.
[Comparative example 8]
The same procedure as in Example 37 was carried out except that B-I was replaced with B-X.
[Comparative Example 9]
The same procedure as in Example 39 was carried out except that IC-819 and OXE-02 were not added.
[Comparative Example 10]
The same procedure as Example 37 was carried out except that BI was not added.
[Comparative Example 11]
The same procedure as in Example 46 was carried out except that B-I was replaced with B-X.
[Comparative example 12]
The same procedure as Example 48 was carried out except that TP5-280M was not added.
[Comparative example 13]
The same procedure as Example 46 was carried out except that BI was not added.
The results of Examples and Comparative Examples are shown in the table below.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulating film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Scribe line 10 Solder bump

Claims (18)

Contains (A) any one or more resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polysiloxane, (B) a thermal base generator, and (C) a photosensitizer. A photosensitive resin composition, 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) contains a photoradical polymerization initiator, the thermal base generator (B) contains a guanidine derivative and/or a biguanide derivative having a quaternary boron anion, and the resin (A) contains a biphenyl structure. A photosensitive resin composition containing a polyimide precursor . The photosensitive resin composition according to claim 1, wherein the resin (A) contains polysiloxane. (A) Any one or more resin selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polysiloxane, (B) thermal base generator, and (C) photosensitive A photosensitive resin composition containing a photoacid generator (c-1), wherein the (B) thermal base generator contains a guanidine derivative and/or a biguanide derivative, and the (C) photosensitive agent contains a photoacid generator (c-1) and a photoacid generator. /or (c-2) A photosensitive resin composition containing a photoradical polymerization initiator, wherein the resin (A) contains polysiloxane. The photosensitive resin composition according to claim 3, wherein the thermal base generator (B) contains a guanidine derivative and/or a biguanide derivative having a quaternary boron anion. The photosensitive resin composition according to claim 3 or 4 , wherein the resin (A) contains a polyimide precursor. The photosensitive resin composition according to any one of claims 1 to 5, wherein the thermal base generator (B) contains a compound represented by general formula (1).

(In general formula (1), R ¹ to R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or an aryl group having 6 to 50 carbon atoms. represents an arylalkyl group of 7 to 50, and Z ⁻ represents a carboxylate or borate anion.) The photosensitive resin composition according to claim 6, wherein Z ^- in the general formula (1) includes a structure of any one of general formulas (2) to (4).

(In general formula (2), R ⁸ to R ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and a 6 to 50 carbon atom represents an aryl group, an arylalkyl group having 7 to 50 carbon atoms, or an alkoxy group having 1 to 50 carbon atoms.)

(In general formula (3), R ¹⁷ to R ²⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and a 6 to 50 carbon atom represents an aryl group, 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.)

(In general formula (4), R ²⁶ to R ²⁹ are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups having 1 to 50 carbon atoms, alkoxy groups having 1 to 50 carbon atoms, and 2 carbon atoms. -50 alkenyl group, C2-50 alkynyl group, C6-50 aryl group, C7-50 arylalkyl group, C7-50 arylalkynyl group, furanyl group, thienyl group, (Indicates pyrrolyl group.) The photosensitive resin composition according to claim 7, wherein Z ^- in the general formula (1) represents the general formula (5).

(In general formula (5), R ³⁰ is a substituted or unsubstituted 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, or an alkenyl group having 2 to 50 carbon atoms. 50 alkynyl group, 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 furanyl group, a thienyl group, or a pyrrolyl group, R ³¹ to R ³³ represents a substituted or unsubstituted aryl group having 6 to 50 carbon atoms.) The photosensitive resin composition according to any one of claims 3 to 8, wherein the resin (A) contains a polyimide precursor having a biphenyl structure. The photosensitive resin composition according to any one of claims 1 to 9, wherein the resin (A) contains a polyimide precursor having a residue of a trivalent or higher amino compound. The photosensitive resin composition according to any one of claims 1 to 10, wherein the (C) photosensitizer contains (c-1) a photoacid generator. The photosensitive agent (C) contains (c-2) a radical photopolymerization initiator, and the (c-2) radical photopolymerization initiator is an alkylphenone compound, an aminobenzophenone compound, a diketone compound, a ketoester compound, or a phosphine oxide. The photosensitive resin composition according to any one of claims 1 to 10, which contains one or more selected from the group consisting of a compound, an oxime ester compound, and a benzoic acid ester compound. The photosensitive resin according to any one of claims 1 to 12, wherein the content of the (B) thermal base generator is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (A) resin. Composition. A photosensitive sheet formed from the photosensitive resin composition according to any one of claims 1 to 13. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 13 or the photosensitive sheet according to claim 14. A step of applying the photosensitive resin composition according to any one of claims 1 to 13 to a substrate, or laminating the photosensitive sheet according to claim 14 on the substrate, and drying to form a photosensitive resin film. A method for producing a cured film, comprising: exposing the photosensitive resin film to light; developing the exposed photosensitive resin film; and heating the developed photosensitive resin film. The method for producing a cured film according to claim 16, wherein the step of heat-treating the developed photosensitive resin film includes a step of heat-treating the photosensitive resin film at a temperature of 170°C or higher and 280°C or lower. An electronic component comprising the relief pattern of the cured film according to claim 15.

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