TWI820180B - Photosensitive resin compositions, photosensitive sheets, their cured films and their manufacturing methods, electronic components - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive resin composition which has good pattern processability, and the cured film cured at low temperature has high chemical resistance, high elasticity, high elongation, and is compatible with metals, especially copper. Has high adhesion. The present invention is a photosensitive resin composition, which contains (A) selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzo Azole, polybenzo A photosensitive resin composition of any one or more resins from the group of azole precursors and polysiloxanes, (B) a thermal base generator and (C) a photosensitizer, wherein the (B) thermal base generator The (C) photosensitive agent contains at least one kind of a guanidine derivative or a biguanide derivative, and the (C) photosensitive agent contains (c-1) a photoacid generator and/or (c-2) a photoradical polymerization initiator.

Description

Photosensitive resin compositions, photosensitive sheets, their cured films and their manufacturing methods, electronic components

The present invention relates to photosensitive resin compositions, photosensitive sheets, their cured films and their manufacturing methods, and electronic components. More specifically, it relates to photosensitive resin compositions, photosensitive sheets, and cured films thereof suitable for surface protective films, interlayer insulating films, and insulating layers of organic electroluminescent elements, etc. for semiconductor elements and the like, and their production. Methods, electronic components.

Typical materials for surface protection films or interlayer insulating films of semiconductor elements, insulating layers of organic electroluminescent elements, and planarizing films of TFT substrates include photosensitivity that can be patterned and has excellent heat resistance, electrical insulation, etc. Polyimide resin. In recent years, as part of a strategy to increase the integration of semiconductors, semiconductor devices using multi-layered metal rewiring have attracted attention. When forming such multi-layer metal rewiring, measures such as lowering the curing temperature of the insulating film are adopted for the purpose of reducing warpage of the base material.

In addition, as a protective film for devices including display devices such as touch screens, highly transparent and high-hardness photosensitive polysiloxanes are being studied. Here, the need to protect base materials with low heat resistance has also increased, and low-temperature hardening of polysiloxane is also desired.

In response to such a need for low-temperature curing, for example, a method of curing at low temperature by combining a soluble polyimide that has been imidized in advance and a cross-linking agent as a photosensitive polyimide is being studied (Patent Document 1) , a method of lowering the thermal curing temperature by imidizing a photobase generator during pattern processing (Patent Document 2), etc. Furthermore, as a photosensitive polysiloxane, a method of combining a siloxane having a highly reactive polymerization group and a polymerization initiator is being studied (Patent Document 3). [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2004/109403 [Patent Document 2] Japanese Patent Application Publication No. 2010-133996 [Patent Document 3] Japanese Patent Application Publication No. 2017-8147

[Problem to be solved by the invention]

Against such a social background, technology that hardens photosensitive insulating materials such as polyimide and polysiloxane at low temperatures is required. However, for example, the technology of Patent Document 1 has difficulty in achieving both chemical resistance and crack resistance of the cured film. The technology of Patent Document 2 has low exposure sensitivity and has problems with reliability and takt time. Furthermore, in the technology of Patent Document 3, sufficient film hardness cannot be obtained from polysiloxane, and storage stability is also poor.

The present invention provides a photosensitive resin that solves the problems associated with the above-mentioned conventional technologies, can form a good pattern by a general photolithography process, and provides a cured film that is cured at a low temperature and has excellent chemical resistance, adhesion, and mechanical properties. composition. [Means used to solve problems]

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

That is, a photosensitive resin composition containing (A) selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzo Azole, polybenzo A photosensitive resin composition of at least one resin from the group of an azole precursor and a polysiloxane, (B) a thermal base generator, and (C) a photosensitizer, wherein the (B) thermal base generator Containing a guanidine derivative and/or a biguanide derivative, the (C) photosensitive agent contains (c-1) a photoacid generator and/or (c-2) a photoradical polymerization initiator.

Moreover, regarding the photosensitive sheet formed from the said photosensitive resin composition.

Moreover, it relates to the cured film which hardened the said photosensitive resin composition or the said photosensitive sheet.

Furthermore, a method for manufacturing a cured film includes the steps of applying the photosensitive resin composition on a substrate or laminating the photosensitive sheet on the substrate and drying it to form a photosensitive resin film; The steps of exposing the photosensitive resin film; subjecting the exposed photosensitive resin film to heat treatment; developing the heat-treated photosensitive resin film; and subjecting the developed photosensitive resin film to heat treatment.

Moreover, it is about the electronic component which has the relief pattern of the said cured film. [Effects of the invention]

The photosensitive resin composition and photosensitive sheet of the present invention have good pattern processability, and the cured film formed by curing the composition at low temperature has excellent chemical resistance, adhesion, and mechanical properties. Furthermore, the electronic component of the present invention has a pattern with excellent adhesion and chemical resistance, and is highly reliable.

[Form used to implement the invention]

The present invention provides a photosensitive resin composition, which contains (A) selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzo Azole, polybenzo A photosensitive resin composition of any one or more resins from the group of azole precursors and polysiloxanes, (B) a thermal base generator and (C) a photosensitizer, wherein the (B) thermal base generator Containing a guanidine derivative and/or a biguanide derivative, the (C) photosensitive agent contains (c-1) a photoacid generator and/or (c-2) a photoradical polymerization initiator. Each ingredient is explained below.

The photosensitive resin composition of the present invention contains (A) selected from the group consisting of epoxy resin, polyimide, polyimide precursor, polybenzo Azole, polybenzo Any one or more resins from the group of azole precursors and polysiloxanes (hereinafter sometimes referred to as "(A) resin"). Among them, it is preferable to contain a polyimide precursor or polysiloxane. Examples of the polyamide precursor used in the resin (A) include polyamide acid, polyamide ester, polyamide acid amide, and polyisoamide imide. Polyamide having a tetracarboxylic acid residue and a diamine residue can be obtained by reacting an acid component with a diamine component. Here, examples of the acid component include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and the like. Examples of the diamine component include diamine, diisocyanate compound, trimethylsilylated diamine, and the like.

As the polyimide precursor of the resin (A), a resin containing a structural unit represented by the following general formula (6) is preferred. Moreover, it does not matter that it contains two or more types of resins which have this structural unit, and it does not matter that it copolymerizes two or more types of structural units. Among them, for the purpose of maintaining exposure sensitivity and reducing the thermal expansion coefficient, a polyimide precursor containing an acid residue or an amine residue having a biphenyl structure is preferred. That is, the resin (A) preferably contains a polyimide precursor having a biphenyl structure. Furthermore, for the purpose of increasing the elastic modulus, the resin (A) is preferably a polyimide precursor containing a residue of an amine compound having a trivalent or higher valence.

In the general formula (6), X represents a 4- 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 any one of a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. p and q independently represent an integer from 0 to 4, r represents an integer from 2 to 8, and s represents an integer from 0 to 8. Among them, regarding p, q, r, and s, when the value is 0, the functional groups in parentheses respectively represent hydrogen atoms. Here, when expressed as "～" in this specification, unless otherwise specified, it means the figure including the upper limit and the lower limit.

In the general formula (6), X is a residue derived from a tetra-, hexa-, octa- or decacarboxylic acid residue or a derivative thereof (hereinafter, these are collectively referred to as "acid residues"). Furthermore, by using an acid component corresponding to this acid residue during polymerization, the structural unit can contain these acid residues. Examples of carboxylic acid compounds having X as an acid residue include: pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 2,3,3',4'-biphenyl Tetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid Formic 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)ethane Methane, bis(3,4-dicarboxyphenyl)terine, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid Formic acid, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids 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-ene tetracarboxylic acid , aliphatic tetracarboxylic acids such as bicyclo[2.2.2.]octanetetracarboxylic acid or adamantanetetracarboxylic acid. Among these, in order to achieve both high exposure sensitivity and low thermal expansion coefficient, 3,3',4,4'-biphenyltetracarboxylic acid and 2,3,3',4'-biphenyltetracarboxylic acid are preferred. Formic acid, 2,2',3,3'-biphenyltetracarboxylic acid. In addition, examples of the acid component having a valence of 6 or higher include the following compounds.

In the above formula, the plural R ^c represents any one of the following structures.

These acids can be used directly or as acid anhydrides, acid chlorides or active esters. Examples of the activated ester group include the following structures, but are not limited thereto.

In the formula, A and D can include hydrogen atoms, methyl, ethyl, propyl, isopropyl, tertiary butyl, trifluoromethyl, halogen, phenoxy, nitro, etc., but are not limited to these. .

Moreover, as a preferable structure of the acid residue of , ester group, nitro group, cyano group, fluorine atom or chlorine atom and substituted structure.

Among them, J represents direct bonding, -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 -OC 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 tetracarboxylic acid containing silicon atoms such as dimethylsilane diphthalic acid or 1,3-bis(phthalic acid)tetramethyldisiloxane, the adhesion to the substrate can be improved and the cleaning properties can be improved. Resistance to oxygen plasma, UV ozone treatment used in etc. These silicon atom-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% of the total acid components.

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

Examples of the amine component having Y as the amine residue include m-phenylenediamine, p-phenylenediamine, 3,5-diamine benzoic acid, 1,5-naphthalenediamine, and 2,6-naphthalenediamine. Amine, 9,10-anthracenediamine, 2,7-diaminofluoride, 4,4'-diamine benzamide benzene, 3,4'-diaminodiphenyl ether, 4,4'-diamine Aminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane , 4,4'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylcarboxylate, 3,4'-Diaminodiphenylcarboxylic acid, 4,4'-Diaminodiphenylcarboxylic acid, 3 ,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 9,9-bis(4-aminobenzene base) fluorine, 1,3-bis(4-anilino)tetramethyldisiloxane, 4,4'-diaminebiphenyl, 2,2'-dimethyl-4,4'-diaminebiphenyl Benzene, 2,2'-diethyl-4,4'-diaminebiphenyl, 3,3'-dimethyl-4,4'-diaminebiphenyl, 3,3'-diethyl-4 ,4'-Diaminebiphenyl, 2,2',3,3'-Tetramethyl-4,4'-Diaminebiphenyl, 3,3',4,4'-Tetramethyl-4,4 '-Diaminebiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminebiphenyl, bis(4-aminophenoxyphenyl)trine, bis(3-amino) Phenoxyphenyl)terine, 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-aminobenzo Azole, 2-(3-aminophenyl)-5-aminobenzo Azole, 2-(4-aminophenyl)-6-aminobenzo Azole, 2-(3-aminophenyl)-6-aminobenzo Azole, 1,4-bis(5-amino-2-benzo Azolyl)benzene, 1,4-bis(6-amino-2-benzo Azolyl)benzene, 1,3-bis(5-amino-2-benzo Azolyl)benzene, 1,3-bis(6-amino-2-benzo Azolyl)benzene, 2,6-bis(4-aminophenyl)benzobis Azole, 2,6-bis(3-aminophenyl)benzobis Azole, bis[(3-aminophenyl)-5-benzo Azolyl], bis[(4-aminophenyl)-5-benzo Azolyl], bis[(3-aminophenyl)-6-benzo Azolyl], bis[(4-aminophenyl)-6-benzo azolyl] and other aromatic diamines, bis(3-amino-4-hydroxyphenyl)trine, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl) Phenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)methene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl) Benzene, 4,4'-diamino-6,6'-bis(trifluoromethyl)-[1,1'-biphenyl]-3,3'-diol, 9,9-bis(3- Amino-4-hydroxyphenyl)fluoride, 2,2'-bis[N-(3-aminobenzyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis [N-(3-Aminobenzyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4-aminobenzyl)-3 -Amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzyl)-3-amino-4-hydroxyphenyl]hexafluoropropane, bis[N -(3-Aminobenzoyl)-3-amino-4-hydroxyphenyl]triane, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl ]碢, 9,9-bis[N-(3-aminobenzyl)-3-amino-4-hydroxyphenyl]fluoride, 9,9-bis[N-(4-aminobenzyl) acyl)-3-amino-4-hydroxyphenyl]fluoride, N,N'-bis(3-aminobenzyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzyl)- 4,4'-Diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxy Diamine phenols such as biphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, etc., with 1 to 10 carbon atoms Compounds in which a part of the hydrogen atoms of these aromatic rings are substituted by alkyl groups, fluoroalkyl groups, halogen atoms, etc., and diamines having the structures shown below, but are not limited to these.

Among these, from the viewpoint of heat resistance, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-diaminebiphenyl, and 2,2-naphthylenediamine are preferred. '-Dimethyl-4,4'-diaminebiphenyl. From the viewpoint of low thermal expansion coefficient, 4,4'-diaminebiphenyl, 2,2'-dimethyl-4,4'-diaminebiphenyl, and 2,2'-diethyl- 4,4'-diaminebiphenyl, 3,3'-dimethyl-4,4'-diaminebiphenyl, 3,3'-diethyl-4,4'-diaminebiphenyl, 2, 2',3,3'-tetramethyl-4,4'-diaminebiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminebiphenyl, 2,2' -Bis(trifluoromethyl)-4,4'-diaminebiphenyl, bis(3-amino-4-hydroxy)biphenyl, 4,4'-diamino-6,6'-bis(tris Fluoromethyl)-[1,1'-biphenyl]-3,3'-diol, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3 ,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis( 4-Aminobenzyl)-3,3'-diamino-4,4-dihydroxybiphenyl. From the viewpoint of elongation, 4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl are preferred. Methane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone. Other diamines to be copolymerized can be used directly or as compounds in which the amine site is isocyanated or trimethylsilylated. Moreover, these 2 or more types of diamine components can also be used in combination.

In addition to the above-mentioned aromatic diamines, aliphatic diamines or diamines having a siloxane structure can also be cited. 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-cyclohexanedi Amine, 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, (the above are product names, HUNTSMAN (stock) ) system) etc. Among the above, it is preferable to include an alkylene oxide structure from the viewpoint of further increasing flexibility and achieving high elongation. In addition, due to the presence of the ether group in the alkylene oxide structure, it can be complexed or hydrogen bonded with the metal, and high adhesion to the metal can be obtained. Furthermore, -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )-, - may also be included. Bonding of N(CH(CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, -NHCONH-, etc.

As diamines with a siloxane structure, bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane can improve the adhesion to the substrate. Sex is better.

In addition to the aforementioned diamine components, trivalent or higher amine compounds can also be cited. Since the resin (A) has a residue of an amine compound having a trivalent or higher valence, the cured film obtained by curing can exhibit a high elastic modulus. Specific examples of the trivalent or higher amine compound include: gin(4-aminophenyl)amine, 1,3,5-gin(4-aminophenoxy)benzene, and 1,3,5-gin(4-aminophenyl)amine. (4-Aminophenyl)benzene, 2,4,4'-triaminodiphenyl ether, 3,4,4'-triaminodiphenyl ether, 2,4,4'-triaminodiphenyl ether Triamino, 3,4,4'-triaminodiphenyl sulfide, 2,4,4'-triaminodiphenyl sulfide, 2,4, 4'-triaminobenzophenone, 3,4,4'-triaminobenzophenone, ginseng(4-aminophenyl)methane, 1,1,1-samino(4-aminobenzene) ethane, 2,4,6-triamino-1,3,5-tris , 2,4,6-shen(4-aminophenoxy)-1,3,5-tri , N ² , N ⁴ , N ⁶ -Shen(4-aminophenyl)-1,3,5-tri -2,4,6 triamine, ginseng(hexylamine)tripolyisocyanate, and triamine, tetraamine or pentamine having the following structures.

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. When the obtained photosensitive resin composition is a positive type, R ^a is preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoint of smaller shrinkage after curing. R ^a and R ^b are preferably hydrogen atoms from the viewpoint of alkali solubility. When the resulting photosensitive resin composition is negative, the organic group having an ethylenically unsaturated bond can improve the exposure sensitivity. Therefore better.

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

As a method for producing the aforementioned tetracarboxylic acid diester, the aforementioned acid dianhydride and alcohol can be directly reacted in a solvent. However, from the viewpoint of reactivity, it is preferable to use a reaction activator. Examples of reaction activators include: pyridine, dimethylaminopyridine, triethylamine, and N-methyl Tertiary amines such as pholine and 1,8-diazabicycloundecene. The addition amount of the reaction activator 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. In addition, a small amount of a polymerization inhibitor may be used for the purpose of preventing cross-linking of ethylenically unsaturated bonding sites during the reaction. Accordingly, in the reaction between alcohols having low reactivity and ethylenically unsaturated bonds and tetracarboxylic dianhydride, the reaction can be accelerated by heating in a range of 120° C. or lower. Examples of the polymerization inhibitor include phenolic compounds such as hydroquinone, 4-methoxyphenol, tertiary butylcatechol, and bis-tertiary butylhydroxytoluene. As the added amount of the polymerization inhibitor, the phenolic hydroxyl group of the polymerization inhibitor is preferably 0.1 mol% or more and 5 mol% or less relative to the ethylenically unsaturated bond of the alcohol.

Various methods can be cited as the aforementioned amide polycondensation reaction. Examples include: a method of chlorinating a tetracarboxylic acid diester and then reacting it with a diamine; a method of using a carbodiimide-based dehydration condensation agent; and a method of activating and esterifying it and then reacting it with a diamine. method.

Examples of the aforementioned alcohols having an ethylenically unsaturated bond include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 1 -(Meth)acryloxy-2-propanol, 2-(meth)acrylamideethanol, hydroxymethylvinylketone, 2-hydroxyethylvinylketone, (meth)acrylic acid 2-hydroxy -3-Methoxypropyl ester, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acrylic acid Hydroxy-3-tertiary butoxypropyl ester, 2-hydroxy-3-cyclohexyl alkoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexyloxypropyl (meth)acrylate, 2 -Alcohols having one ethylenically unsaturated bond and one hydroxyl group, such as (meth)acryloxyethyl-2-hydroxypropyl phthalate, glycerol-1,3-di(meth)acrylate , Glycerin-1,2-di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentylerythritol tri(meth)acrylate, dineopenterythritol penta(meth)acrylate Acrylate, glycerol-1-allyloxy-3-methacrylate, glycerol-1-allyloxy-2-methacrylate, 2-ethyl-2-(hydroxymethyl)propane-1 , 3-diyl bis(2-methacrylate), 2-((acrylyloxy)-2-(hydroxymethyl)butyl methacrylate, etc., which have more than 2 ethylenically unsaturated bonds and 1 Alcohols with a hydroxyl group, etc. Here, "(meth)acrylate" means 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 together. Other alcohols can be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in organic solvents. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, 1-pentanol, 2-pentanol, Aliphatic alcohols such as 3-pentanol and isoamyl alcohol, or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether and other alkylene oxide-derived monools.

In general formula (6), as another method of introducing an organic group having 1 to 20 carbon atoms in R ^a , for example, polyamide acid is obtained from an acid dianhydride and a diamine, and then esterified by a conventional method. Methods. Examples of the esterification reaction include a method using a compound having trifluoroacetic acid and a hydroxyl group, a method of reacting dimethylformamide dialkyl acetal, and the like.

In addition, in order to improve the storage stability of the photosensitive resin composition of the present invention and to exhibit various functions, a terminal blocking agent may be used to block the main chain terminal of the resin (A). Examples of end-capping agents include monoamines, acid anhydrides, monocarboxylic acids, monochloride compounds, and monoactive ester compounds. Furthermore, in the later stage of the reaction of the aforementioned amide polycondensation, a monoalcohol may be used as a terminal blocking agent. In addition, by blocking the ends of the resin with an end-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 speed and exposure sensitivity of the resin to an alkali solution can be easily improved. , the mechanical properties of the obtained cured film are adjusted to a better range.

The introduction ratio of the terminal blocking 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 the solubility of the developer and the mechanical properties of the obtained cured film. It is also possible to react a plurality of end-capping agents to introduce a plurality of different terminal groups.

As the monoamine used as the end-capping agent, preferred are M-600, M-1000, M-2005, M-2070 (the above are trade names, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, 3 -Ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene Naphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalic acid, 5-aminosalic acid, 6-aminobenzene sulfonate Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminephenol, 3-aminephenol, 4-aminephenol, 2-aminebenzene Thiol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more types of these may be used.

As the acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, and 3-carboxylic anhydride are preferred. Phenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1- Monocarboxylic acids such as mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. and these carboxyl groups have been chlorinated Chemical monochloride compounds, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, A monochloride compound in which only one carboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene is chlorinated. The monochloride compound is combined with N-hydroxybenzotriazole, imidazole, and N-hydroxy-5-norbornene. -Active ester compounds obtained from the reaction of 2,3-dicarboxylimide, etc. Two or more types of these may be used.

Examples of the monoalcohol used as the end-capping agent include alcohols that react with the aforementioned acid anhydride.

In addition, the end-capping agent introduced into the resin (A) used in the present invention can be easily detected by the following method. For example, the resin into which the end-capping agent has been introduced is dissolved in an acidic solution, decomposed into the amine component and the acid anhydride component of the structural units, and measured using gas chromatography (GC) or NMR, whereby the present invention can be easily detected. The capping agent used. In addition, each component and an external standard material whose peaks do not overlap are simultaneously measured by GC. By comparing the integrated value of each peak in the chromatogram with the external standard material, the molar ratio of each monomer containing the blocking agent can be estimated. In addition, it can also be easily detected by directly measuring the resin components into which the end-capping agent has been introduced using thermal decomposition gas chromatography (PGC), infrared spectroscopy, ¹ H-NMR spectroscopy, ¹³ C-NMR spectroscopy and 2-dimensional NMR spectroscopy. . In this case, the molar ratio of each monomer can be analyzed from the integrated value of the infrared spectrum, ¹ H-NMR spectrum, or 2-dimensional NMR.

Polyimide as the resin (A) can be obtained by subjecting a polyimide precursor to partial dehydration and ring-closure by heat treatment or chemical treatment with acid, alkali, or the like. More specifically, the heat treatment may be performed by adding a solvent that is azeotropic with water, such as m-xylene, or the heat treatment may be performed at a low temperature of 100° C. or lower by adding a weakly acidic carboxylic acid compound. Examples of the ring-closing catalyst used in the chemical treatment include dehydration condensation agents such as carboxylic anhydride and dicyclohexylcarbodiimide, and bases such as triethylamine. Moreover, it can be obtained by polymerizing an amine compound or a carboxylic acid compound containing a acyl imine group as a residue as a monomer.

唑前驅物，可列舉例如：與多羥基醯胺、多胺基醯胺、聚醯胺或聚醯胺醯亞胺的共聚物，但較佳為多羥基醯胺。具有二羧酸殘基與雙胺苯酚殘基的多羥基醯胺，可使雙胺苯酚與二羧酸或對應之二羧醯氯或二羧酸活性酯等反應而得。 Polybenzo as (A) resin

Examples of the azole precursor include copolymers with polyhydroxyamide, polyaminoamide, polyamide, or polyamideimide, but polyhydroxyamide is preferred. Polyhydroxyamides having dicarboxylic acid residues and diaminephenol residues can be obtained by reacting diaminephenol with dicarboxylic acid or the corresponding dicarboxylic acid chloride or dicarboxylic acid active ester.

Examples of the dicarboxylic acid used as a monomer of the polyhydroxyamide include cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, and isopropylpropylpropane Diacid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid 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, pimelic acid, 2,2,6,6-tetramethylpimelic acid, Suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid Acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid Acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid , triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid and other aliphatic dicarboxylic acids, terephthalic acid, metaphthalic acid, diphenyl ether dicarboxylic acid , bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid or triphenyldicarboxylic acid and other aromatic dicarboxylic acids. In addition, tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, or diphenyl tricarboxylic acid can also be used. Examples of the diamine phenol include those exemplified among the aforementioned amine components having Y as an amine residue.

Polybenzo as (A) resin From the viewpoint of solubility, azole is preferably a copolymer with other resins. For example, by pre-using benzo By polymerizing a polyimide precursor with an amine compound or a carboxylic acid derivative as a monomer in the azole moiety as a residue, a polyimide precursor-polybenzo can be obtained. Azole copolymer.

Moreover, (A) resin may be a copolymer. Among them, preferred are polyimide precursor-polyimide copolymer, polyimide precursor-polybenzo Azole precursor copolymer. The polyimide precursor-polyimide copolymer can be obtained by subjecting a part of the polyimide precursor to thermal or chemical imidization during polymerization. Polyimide precursor-polybenzo The azole precursor copolymer can be obtained by polymerizing the polyhydroxyamide during and/or before and/or before the reaction for obtaining the polyimide precursor. Alternatively, it can also be obtained by polymerizing a polyimide precursor using an amine compound or a carboxylic acid compound having a hydroxyamide moiety as a residue as a monomer in advance.

Examples of the epoxy resin of the resin (A) include resins obtained by glycidifying a phenolic compound. Examples of phenolic compounds include bisphenol A, bisphenol F, bisphenol E, bisphenol AF, bisphenol S, bisphenol quinone, biphenol, bisphenolmethane, α,α,α'-bisphenol ( Low molecular compounds such as 4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and phenol resins including novolac resins obtained by the polycondensation of phenolic low molecular compounds and aldehyde compounds, but Not limited to this. Among these, resins obtained by glycidifying bisphenol A-modified phenol resin and novolak resin are preferred because of their excellent reactivity.

The polysiloxane as the resin (A) is a hydrolysis/dehydration condensation product of organosilane, and in the present invention, it is preferred that it has a hydrophilic group. By having a hydrophilic group in polysiloxane, developability can be further improved and development residue can be further suppressed. Furthermore, it is more preferable to have a styrene group. By having a styrene group in polysiloxane, the hardness and chemical resistance can be further improved.

Examples of the hydrophilic group include a carboxyl group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, a hydroxyl imide group, and the like. You may have 2 or more types of these. Among these, a carboxyl group and a carboxylic anhydride group are preferable, and a carboxylic anhydride group is more preferable from the viewpoint of further suppressing development residue and further improving storage stability.

Polysiloxane having a hydrophilic group and a styrene group can be obtained, for example, by hydrolysis and dehydration condensation of a plurality of organosilane compounds including an organosilane compound having a hydrophilic group and an organosilane compound having a styrene group. . Organosilane compounds other than organosilane compounds having hydrophilic groups and radically polymerizable groups may be hydrolyzed and dehydrated together with these.

As the organosilane compound having a hydrophilic group, an organosilane compound having a carboxylic acid group and/or a carboxylic anhydride group is preferred, and an organosilane compound having a carboxylic anhydride group is more preferred. Examples include: 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, trimethoxysilylpropylcyclohexane Hexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, etc.

Polysiloxane having a styrene group can be obtained, for example, by hydrolysis and dehydration condensation of a plurality of organosilane compounds including an organosilane compound having a styrene group. As the organosilane compound having a styryl group, styryltrimethoxysilane and styryltriethoxysilane are preferred, and styryltrimethoxysilane is more preferred. Examples of organosilane compounds other than organosilane compounds having a hydrophilic group and a styrene group include methyltrimethoxysilane, methyltriethoxysilane, and methyltris(methoxyethoxysilane). )silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, Octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl )-3-Aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidoxysilane Propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane Silane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane Silane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-cyclohexane Oxypropoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyl Triisopropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltris(methoxyethoxy)silane, α-glycidoxybutyl Trimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltrimethoxysilane Butyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4- Epoxycyclohexyl)ethyl tripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-cyclohexyl) Oxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldi Methyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amine Propylmethyldimethoxysilane, Glycidoxymethyldimethoxysilane, Glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyl Dimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethane diethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropyl Methyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Methyl diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldibutoxysilane Propylmethyldi(methoxyethoxy)silane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane Silane, tetraethoxysilane, etc. Two or more types of these may be used.

Polysiloxane can be obtained by hydrolyzing the aforementioned organosilane compound and subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or in the absence of a solvent.

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

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

When an acid catalyst is used in the hydrolysis reaction, the amount of the acid catalyst added is preferably: 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. 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, and more preferably 10 parts by mass or less based on 100 parts by mass of all the alkoxysilane compounds. . Here, the amount of all alkoxysilane compounds means the amount including all alkoxysilane compounds, hydrolysates and condensates thereof. The hydrolysis reaction can be carried out in a solvent.

The solvent can be appropriately selected taking into consideration the stability, wettability, volatility, etc. of the photosensitive siloxane resin composition. Among these, from the viewpoint of the penetration rate and crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like are preferably used. Propylene glycol monobutyl ether, propylene glycol monotertiary butyl ether, γ-butyrolactone, etc.

When a solvent is generated due to a hydrolysis reaction, hydrolysis can also be performed without a solvent. After the hydrolysis reaction is completed, it is also preferable to adjust the concentration to an appropriate concentration by adding more solvent to prepare a photosensitive resin composition. Moreover, after hydrolysis, the total amount or part of the alcohol etc. produced may be distilled off and removed by heating and/or under reduced pressure, and then an appropriate solvent may be added.

When a solvent is used in the hydrolysis reaction, the amount of the solvent added is preferably 50 parts by mass or more, and more preferably 80 parts by mass based on 100 parts by mass of all the alkoxysilane compounds, from the viewpoint of suppressing the formation of colloids. above. On the other hand, the added amount of the solvent is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less based on 100 parts by mass of all the alkoxysilane compounds, from the viewpoint of making hydrolysis proceed more quickly.

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

Examples of the dehydration condensation reaction method include a method of directly heating a silicon alcohol compound solution obtained by a hydrolysis reaction of an organosilane compound. 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. In addition, in order to increase the degree of polymerization of polysiloxane, reheating or addition of an alkali catalyst may be performed. In addition, according to the purpose, after hydrolysis, an appropriate amount of the generated alcohol and the like can be distilled off and removed by heating and/or under reduced pressure, and then an appropriate solvent can be added.

From the viewpoint of the storage stability of the polysiloxane, it is preferred that the polysiloxane solution after hydrolysis and dehydration condensation does not contain the aforementioned catalyst, and the catalyst can be removed as required. As a method for removing the catalyst, from the viewpoint of ease of operation and removability, water washing, treatment with an ion exchange resin, etc. are preferred. The so-called water washing is a method of diluting the polysiloxane solution with an appropriate hydrophobic solvent, washing it with water several times, and concentrating the obtained organic layer with an evaporator or the like. The so-called treatment with ion exchange resin is a method of contacting a polysiloxane solution with an appropriate ion exchange resin.

The resin (A) in the present invention preferably has a weight average molecular weight of 5,000 to 100,000. By setting the weight average molecular weight to 5,000 or more in polystyrene conversion using GPC (Gel Permeation Chromatography), mechanical properties such as elongation after hardening, breaking point strength, and elastic modulus 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 mechanical properties, it is more preferably 20,000 or more. Moreover, when (A) resin contains 2 or more types of resins, it is sufficient as long as the weight average molecular weight of at least 1 type is in the said range.

Furthermore, the resin (A) used in the present invention is preferably polymerized using a solvent. The polymerization solvent is not particularly limited as long as it can dissolve acid components, amine components, alcohols, and catalysts in the raw material monomers. Examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone , N,N'-dimethylpropyl urea, N,N-dimethylisobutyric acid amide, amide of methoxy-N,N-dimethylpropyl amide, γ-butylidene esters, cyclic esters such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethylene carbonate, and propylene carbonate Carbonates such as triethylene glycol, diols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, cyclotenine, dimethyl sulfoxide, etc.

The photosensitive resin composition of the present invention contains (B) a thermal base generator. The aforementioned (B) thermal base generator is a guanidine derivative and/or a biguanide derivative (hereinafter, may be abbreviated as "(B) component"). By containing component (B), the ring-closing reaction of resin (A) can be accelerated in the thermal hardening step, and polyimide can be obtained even in a low-temperature region below 250°C. Thereby, the mechanical properties of the cured film formed by curing the photosensitive resin composition of the present invention can be improved, especially the elongation and breaking point strength. In addition, the adhesion between the cured film and the metal base layer can be improved. The thermal base generator (B) preferably contains a guanidine derivative and/or a biguanide derivative having a quaternary boron anion. (B) The component can be classified into nonionic and ionic, but ionic base generators are preferred because of their high activity. In addition, biguanide derivatives are preferred because the base generated has high alkalinity. Among these, compounds represented by general formula (1) are particularly preferred.

In the general formula (1), R ¹ to R ⁷ are each independently a hydrogen atom, and represent an 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, either all of which are substituted or unsubstituted. Alkyl, 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, and examples thereof include methyl, ethyl base, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, cyclobutyl, n-pentyl, isopentyl, secondary pentyl, tertiary pentyl, Neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, n-hexyl, isohexyl, secondary hexyl, tertiary hexyl, neohexyl, 2 -Methylpentyl, 1,2-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, secondary heptyl, tris Secondary heptyl, neoheptyl, cycloheptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, neooctyl, 2-ethylhexyl, cyclooctyl, n-nonyl, isononyl Base, secondary nonyl, tertiary nonyl, neononyl, cyclononyl, n-decyl, isodecyl, secondary decyl, tertiary decyl, neodecyl, cyclodecyl, n-undecanyl , cyclodecyl, n-dodecayl, cyclodecyl, norbornyl, Bornyl, eryl, isobornyl, adamantyl, etc. Among these, particularly from the viewpoint of the stability and solubility of the compound, methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, and 2-ethylhexyl are preferred.

The aryl group having 6 to 50 carbon atoms may be either monocyclic or condensed polycyclic. Specific examples thereof include phenyl, naphthyl, anthracenyl, phenanthrenyl, and the like.

The aralkyl group having 7 to 50 carbon atoms may be either a monocyclic type or a condensed polycyclic type. Specific examples include benzyl group, phenethyl group, methylbenzyl group, and phenylpropyl group. , 1-methylphenylethyl, phenylbutyl, 2-methylphenylpropyl, tetrahydronaphthyl, naphthylmethyl, naphthylethyl, indenyl, benzyl, anthracenylmethyl, Phenanthylmethyl etc.

In the general formula (1), the organic groups represented by R ¹ to R ⁷ may be substituted if they are other than hydrogen atoms. Examples of the substituent of the alkyl group having 1 to 50 carbon atoms include amino group, nitro group, epoxy group, alkoxycarbonyl group, vinyl group, (meth)acrylyl group, ethynyl group, and coumarinylcarbonyl group. , anthraquinone group, xanthonyl group (xanthonyl) and thioxanthonyl group (thioxanthonyl). Specific examples of the epoxy group include glycidyl group and 2,3-cyclohexylepoxyethyl group. Specific examples of the alkoxycarbonyl group include: methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, n-isobutoxycarbonyl group, secondary butyl group Oxycarbonyl, tertiary butoxycarbonyl, cyclobutoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, neopentyloxycarbonyl, 2 -Methylbutoxycarbonyl, 1,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, cyclopentoxycarbonyl, etc. Specific examples of the amino group include, in addition to the unsubstituted primary amino group, methylamino group, dimethylamino group, ethylamine group, diethylamine group, n-propylamine group, di-n-propylamine group, and isopropylamine group. base, diisopropylamine base, n-butylamine base, di-n-butylamine base, isobutylamine base, diisobutylamine base, secondary butylamine base, di-secondary butylamine base, tertiary butylamine base, A secondary or tertiary amine group substituted with an alkyl group having 1 to 4 carbon atoms, such as a di-tertiary butylamine group, a cyclobutylamine group, or a dicyclobutylamine group.

Examples of the substituent of an aryl group having 6 to 50 carbon atoms or an aralkyl group having 7 to 50 carbon atoms include an alkyl group, an alkoxy group, a coumarinylcarbonyl group, an anthraquinone group, a xanthonyl group, and a thiophenyl group. Anthone group, halogen atom and nitro group. The alkyl group may be linear, branched or cyclic, and specific examples include the alkyl groups having 1 to 50 carbon atoms described above. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, tertiary butoxy, cyclic Butoxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, neopentyloxy, 2-methylbutoxy, 1,2-dimethylpropoxy, 1-ethylpropoxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, secondary hexyloxy, tertiary hexyloxy, neohexyloxy, 2-methylpentyloxy, 1,2- Dimethylbutoxy, 2,3-dimethylbutoxy, 1-ethylbutoxy, cyclohexyloxy, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

In the general formula (1), Z ^- represents the anion of a carboxylic acid ester or a boric acid ester. Examples of carboxylic acid esters that impart Z ^- include aliphatic carboxylic acids derived from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, etc. Carboxylic acid esters of aromatic carboxylic acid compounds such as benzoic acid, 4-benzoylbenzoic acid, salicylic acid, cinnamic acid, and 4-bibenzoic acid. Furthermore, carboxylic acid esters represented by general formula (2) and general formula (3) can be used, and are preferred 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 each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or Aralkyl group having 7 to 50 carbon atoms or alkoxy group having 1 to 50 carbon atoms.

In the general formula (3), R ¹⁷ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or An aralkyl 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 the general formula (2) and R ¹⁷ to R ²⁵ in the general formula (3) may be linear, branched or cyclic. Specific examples of any of them include those exemplified by the alkyl group having 1 to 50 carbon atoms represented by R ¹ to R ⁷ in the general formula (1). The same applies to the substituents in the case of substitution. Examples of the aryl group having 6 to 50 carbon atoms and the aralkyl group having 7 to 15 carbon atoms include those exemplified in the description of R ¹ to R ⁷ in the general formula (1). Substituents in the case of substitution Same thing. 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, secondary butoxy group, tributoxy group, etc. Primary butoxy, cyclobutoxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, neopentyloxy, 2-methylbutoxy, 1,2-di Methylpropoxy, 1-ethylpropoxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, secondary hexyloxy, tertiary hexyloxy, neohexyloxy, 2-methylpentyloxy base, 1,2-dimethylbutoxy, 2,3-dimethylbutoxy, 1-ethylbutoxy, cyclohexyloxy, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

In the general formula (1), as the borate ester that imparts ^Z- , there are those containing hydrogen atoms or halogen atoms, such as tetrahydroborate, tetrafluoroborate, tetrachloroborate, tetrabromoborate, etc. In addition to boric acid esters, boric acid esters represented by the following general formula (4) are also preferred from the viewpoint of storage stability.

In the general formula (4), R ²⁶ to R ²⁹ represent 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 alkoxy group having 2 to 50 carbon atoms. Alkenyl group, alkynyl group having 2 to 50 carbon atoms, aryl group having 6 to 50 carbon atoms, aralkyl group having 7 to 50 carbon atoms, arylalkynyl group having 7 to 50 carbon atoms, furyl group, thienyl group or pyrrolyl group.

As R ²⁶ to R ²⁹ in the general formula (4), it is an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, and an alkyl group having 7 to 50 carbon atoms. Examples of the aralkyl group include those exemplified in the description of R ¹ to R ⁷ in the general formula (1), and the substituents in the case of substitution are also the same. Examples of the alkenyl group having 2 to 50 carbon atoms include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and isobutylene. base, methacrylyl, isoprenyl, isopentenyl, cyclopentenyl, n-hexenyl, cyclohexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decyl Alkenyl, n-undecenyl, n-dodecenyl, etc.

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

Examples of the arylalkynyl group having 7 to 50 carbon atoms include phenylethynyl, 3-phenylpropynyl, 4-phenylbutynyl, 5-phenylpentynyl, and 6-phenylhexynyl. base. The pyrrolyl group may also be an N-substituted form. Examples include: N-methylpyrrolyl, N-ethylpyrrolyl, N-n-propylpyrrolyl, N-isopropylpyrrolyl, and N-n-butylpyrrolyl. base, N-isobutylpyrrolyl, N-secondary butylpyrrolyl, N-tertiary butylpyrrolyl, N-cyclobutylpyrrolyl, N-n-pentylpyrrolyl, N-isopentylpyrrolyl base, N-secondary pentylpyrrolyl, N-tertiary pentylpyrrolyl, N-neopentylpyrrolyl, N-cyclopentylpyrrolyl, N-n-hexylpyrrolyl, N-isohexylpyrrolyl, N-secondary hexylpyrrolyl, N-tertiary hexylpyrrolyl, N-neohexylpyrrolyl, N-2-methylpentylpyrrolyl, N-cyclohexylpyrrolyl, etc.

The organic groups represented by R ²⁶ to R ²⁹ in the general formula (4) may be substituted in addition to hydrogen atoms and halogen atoms. Specific examples of the substituents of the alkyl group having 1 to 50 carbon atoms, the aryl group having 6 to 50 carbon atoms, and the aralkyl group having 7 to 50 carbon atoms are represented by R ¹ to R ⁷ in the general formula (1), respectively. The organic bases are the same as those mentioned above. Among them, a halogen atom or a nitro group is preferred, and fluorine is more preferred. Examples of substituents of alkenyl groups having 2 to 50 carbon atoms, alkynyl groups having 2 to 50 carbon atoms, arylalkynyl groups having 7 to 50 carbon atoms, furyl groups, thienyl groups, and pyrrolyl groups include those having 6 to 50 carbon atoms. The substituents of the aryl groups are the same.

Among the borate anions represented by the general formula (4), the one represented by the following general formula (5) is preferable because it has better storage stability.

In the general formula (5), R ³⁰ represents 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. Alkynyl group, aryl group with 6 to 50 carbon atoms, aralkyl group with 7 to 50 carbon atoms, arylalkynyl group with 7 to 15 carbon atoms, furyl group, thienyl group or pyrrolyl group, R ³¹ to R ³³ represent carbon number 6 ~50 aryl group.

Furthermore, in the general formula (5), the aryl groups of R ³¹ to R ³³ are more preferably substituted with electron withdrawing groups. Examples of the electron-withdrawing group include fluorine atom, chlorine atom, bromine atom, nitro group, etc., among which a fluorine atom is preferred. In addition, when each of the alkyl group having 1 to 50 carbon atoms and the aryl group having 6 to 50 carbon atoms contains one or more, the solubility in the organic solvent is high, which is preferable.

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

Specific examples of the component (B) include any combination of the specific examples of the aforementioned biguanide cation and the specific examples of the carboxylate anion or the borate anion. 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 phosphate. En, benzoic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 2-(9-oxophenylquinone-2-yl)propionic acid 1,5,7-triazo Heterobicyclo[4.4.0]dec-5-ene, 2-(3-benzylphenyl)guanidine propionate, guanidine acetate, guanidine phosphate, guanidine benzoate, L-arginine, L-spermine acetate Acid, L-arginine phosphate, L-arginine benzoate, etc.

The content of component (B) is not particularly limited, but is preferably from 0.1 to 10 parts by mass relative to 100 parts by mass of the polyimide precursor (A). Within this range, on the one hand, the ring-closing reaction of the polyimide precursor (A) can be promoted, and on the other hand, the pattern processability, solubility, and storage stability can be appropriately maintained. It is preferably 0.3 parts by mass or more and 7 parts by mass or less, and 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 photosensitive agent. The aforementioned (C) photosensitizer contains (c-1) photoacid generator and/or (c-2) photoradical polymerization initiator. By containing the photosensitive agent (C), pattern processing can be performed through exposure and development steps.

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

Examples of the quinonediazide compound include those in which sulfonic acid of quinonediazide is ester-bonded with a polyhydroxy compound, and those in which sulfonic acid of quinonediazide is ester-bonded with a polyamine compound. , quinonediazide sulfonic acid and polyhydroxypolyamine-based compounds are bonded by ester bonding and/or sulfonamide bonding, etc. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but it is preferable that on average at least 40 mol% of the total functional groups are substituted with quinonediazide. replace. By using such a quinonediazide compound, a positive-type photosensitive resin composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of a general ultraviolet mercury lamp can be obtained .

Polyhydroxy compounds, including: Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene ginseng-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, 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 (the above are trade names, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR- PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, manufactured by Asahi Organic Materials Co., Ltd. ), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, Naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but not limited to And so on.

Polyamine compounds include: 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, etc., but are not limited to these.

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

Among these, the quinonediazide compound is more preferably an ester containing a phenol compound and a 4-naphthoquinonediazide sulfonyl group. As a result, high sensitivity and higher resolution can be obtained in i-ray exposure.

(c-1) The content of the photoacid generator is preferably 1 part by mass or more to obtain sufficient sensitivity after exposure, more preferably 10 parts by mass or more based on 100 parts by mass of the polyimide precursor (A) . In addition, the content of the quinonediazide compound is preferably 50 parts by mass or less without degrading the film properties, more preferably 40 parts by mass or less based on 100 parts by mass of the polyimide precursor (A). By setting the content of the quinonediazide compound within this range, it is possible to achieve higher sensitivity while obtaining target film characteristics.

Furthermore, other photoacid generators or sensitizers such as onium salts, diaryl compounds, iminosulfonium salts, etc. can also be added according to needs. In addition, by using an onium salt as the component (B), it can also function as a photocuring agent for epoxy resin. By using onium salts in epoxy resin, negative patterns can be obtained. Examples of the onium salt include aromatic iodonium salts and aromatic iodonium salts. Among them, specific examples of aromatic iodonium salts include diphenyliodonium tetra(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, and diphenyliodonium hexafluoroantimony. Acid ester, bis(4-nonylphenyl)iodonium hexafluorophosphate, tolyl Ionium tetra(pentafluorophenyl)borate (manufactured by Rohdia, trade name: Rhodorsil Photoinitiator 2074), di(4-tertiary butyl)iodonium methyl (trifluoromethanesulfonyl) methylate (BASF Japan Company system, product name CGI BBIC C1), etc.

As a specific example of the aromatic sulfonium salt, 4-(phenylthio)phenyldiphenylsonium hexafluoroantimonate (manufactured by SAN-APRO Co., Ltd., trade name: CPI-101A ), 4-(phenylthio)phenyldiphenylgin (pentafluoroethyl) trifluorophosphate (manufactured by SAN-APRO Co., Ltd., trade name CPI-210S), 4-{4-(2 -Chlorobenzyl)phenylthio}phenylbis(4-fluorophenyl)sonium hexafluoroantimonate (manufactured by Asahiden Chemical Co., Ltd., trade name SP-172), containing 4-(phenyl) A mixture of aromatic sulfonium hexafluoroantimonate (manufactured by Dow Chemical Co., Ltd., trade name UVI-6976) and triphenyl sulfonate (trifluoromethanesulfonate) ) methyl compound (manufactured by BASF Japan, trade name: CGI TPS C1), ginseng [4-(4-ethylphenylhydrothio)phenyl] ginseng [(trifluoromethyl)sulfonyl]methane base compound (manufactured by BASF Japan Co., Ltd., trade name GSID26-1), ginseng[4-(4-ethylphenyl)thiophenyl]ethyl(pentafluorophenyl)borate (manufactured by BASF Japan Co., Ltd., Product name PAG-290), etc.

The aforementioned (c-2) photoradical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by exposure, but alkylphenone compounds, aminobenzophenone compounds, diketone compounds, Ketone ester compounds, phosphine oxide compounds, oxime ester compounds, and benzoate ester compounds are preferred because they have excellent sensitivity, stability, and ease of synthesis. Among them, from the viewpoint of sensitivity, alkylphenone compounds and oxime ester compounds are preferred, and oxime ester compounds are particularly preferred. In addition, when processing a thick film having a film thickness of 5 μm or more, a phosphine oxide compound is preferred from the viewpoint of resolution. By containing (c-2) a photoradical polymerization initiator, a negative pattern can be obtained.

Examples of alkylphenone compounds include: 2-methyl-[4-(methylthio)phenyl]-2- Oxylinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Phin-4-yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4- Alpha-aminoalkylphenone compounds such as linylphenyl)-butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylbenzene base)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2-hydroxy-1-{4 -[4-(2-Hydroxy-2-methyl-propyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl-phenyl ketone, benzoin α-hydroxyalkylphenone compounds, 4-benzoyl-4-methylphenylketone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-benzene, etc. 2-Phenylacetophenone, 2-hydroxy-2-methylpropylbenzene, p-tertiary butyldichloroacetophenone, benzylmethoxyethyl acetal, 2,3-diethoxy α-alkoxyalkylphenone compounds such as benzoacetophenone, benzyldimethyl ketal, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetophenone, p-tris Acetophenone compounds such as butyl dichloroacetophenone. Among these, 2-methyl-[4-(methylthio)phenyl]-2- Oxylinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Phin-4-yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4- α-aminoalkylphenone compounds such as linylphenyl)-butanone-1 are preferred because of their high sensitivity.

Examples of the phosphine oxide compound include: 6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis( 2,6-Dimethoxybenzyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

Examples of the oxime ester compound include: 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime Methoxycarbonyl) oxime, 1-phenyl-2-(benzoyl oxime imino)-1-propanone, 2-octanedione, 1-[4-(phenylthio)-2-( o-benzoyl oxime)], 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl) oxime, 1,3-diphenylglycerol-2-(o-ethoxy Carbonyl) oxime, ethanone, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-phenyl-3-ethoxyglycerol-2-(o-benzyl) Benzyl) oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime), 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyl oxime), NCI-831, NCI-930 (above Made by ADEKA), OXE-03, OXE-04 (the above are made by BASF), etc. Among these, from the viewpoint of sensitivity, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-( 0-acetyl oxime), 2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], NCI-831, NCI-930, OXE-03, OXE -04.

Examples of the aminobenzophenone compound include 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone. Examples of the diketone compound include benzoethylene glycol. Examples of the ketoester compound include methyl benzoate and ethyl benzoate.

Examples of benzoate compounds include: methyl o-benzoate, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and p-diethyl Ethyl aminobenzoate.

Other specific examples of the (c-2) photoradical polymerization initiator include benzophenone, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and Ketone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated dibenzophenone Benzophenone, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)benzophenone, bromide-4-benzoyl-N,N-dimethyl-N- [2-(1-Oxo-2-propenyloxy)ethyl]benzylamine, (4-benzylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4) chloride -Benzoylphenoxy)-N,N,N-trimethyl-1-propylammonium monohydrate, 9-oxosulfide , 2-Chloro-9-oxysulfide ,2,4-Dichloro9-oxosulfide , 2-Methyl 9-oxosulfide , 2-isopropyl 9-oxosulfide , 2,4-dimethyl 9-oxosulfide , 2,4-diethyl 9-oxosulfide , 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-sulfide chloride -2-yloxy)-N,N,N-trimethyl-1-propylammonium, anthraquinone, 2-tertiary butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone , benzanthrone, dibenzocycloheptanone, methyleneanthrone, 4-azidobenzylideneacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2 , 6-bis(p-azidobenzylidene)-4-methylcyclohexanone, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, Triphenylphosphine, carbon tetrabromide, tribromophenyltrine, etc.

As the content of the (c-2) photoradical polymerization initiator, the sum of the (A) resin and the compound having two or more ethylenically unsaturated bonds (D) mentioned later if necessary is 100 mass. In the case of parts by mass, 0.5 parts by mass or more and 20 parts by mass or less is preferred because sufficient sensitivity can be obtained and the amount of outgassing during thermal hardening can be suppressed. Among them, the content is more preferably 1.0 parts by mass or more and 10 parts by mass or less.

The photosensitive resin composition of the present invention may also contain a sensitizer for the purpose of improving the function of the (c-2) photoradical polymerization initiator. By containing a sensitizer, the sensitivity can be increased and the photosensitive wavelength can be adjusted. Examples of sensitizers include bis(dimethylamino)benzophenone, bis(diethylamino)benzophenone, and diethyl 9-oxosulfide. , N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methylcoumarin, N- phenyl Phenolines and their derivatives, etc., but are not limited to these.

In the case of negative type, the photosensitive resin composition of the present invention may contain (D) a compound having two or more ethylenically unsaturated bonds (hereinafter sometimes abbreviated as "(D) component"). By containing component (D), the exposure sensitivity is further improved because the cross-linking density during exposure is increased. In addition, the chemical resistance of the hardened cured film is further improved. Furthermore, as will be described later, by selecting a molecular structure according to the purpose, various functions such as hydrophobicity and elongation can be added.

Examples of the component (D) include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol. Di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-butanediol di(meth)acrylate, new Pentylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol di(meth)acrylate ) Acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate , Neopenterythritol tri(meth)acrylate, Neopenterythritol tetra(meth)acrylate, Dineopenterythritol penta(meth)acrylate, Dineopenterythritol hexa(meth)acrylate , Trineopenterythritol hepta(meth)acrylate, Trineopenterythritol octa(meth)acrylate, Tetraneopenterythritol nona(meth)acrylate, Tetraneopenterythritol ten(meth)acrylate Acrylate, penta-neopenterythritol undeca(meth)acrylate, penta-neopenterythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9- Bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorine, (2-(meth)acryloxypropoxy)-3-methylphenyl]fluorine or 9 ,9-bis[4-(2-(meth)acryloxyethoxy)-3,5-dimethylphenyl]fluoride.

When the exposure sensitivity is to be further improved, neopentyl tetraacrylate, dineopenterythritol pentaacrylate, dineopenterythritol hexaacrylate, trineopenterythritol heptaacrylate or trineopenterythritol is preferred. Tetraol octaacrylate; in order to improve the adhesion during development by improving hydrophobicity, dimethylol-tricyclodecane diacrylate or dimethylol-tricyclodecane dimethyl is preferred. acrylate, ethoxylated bisphenol A diacrylate or 9,9-bis[4-(2-propenyloxyethoxy)phenyl]fluorine; if you want to increase the elongation of the cured film, Preferred are tetraethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate.

Examples of the compound of other component (D) include epoxy (meth)acrylate obtained by reacting a polyfunctional epoxy compound and (meth)acrylic acid. Because epoxy (meth)acrylate has added hydrophilicity, it can be used to improve alkali developability. Examples of polyfunctional epoxy compounds include the following compounds. These polyfunctional epoxy compounds are preferred 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. As long as it is 5000 or less, the compatibility with the resin (A) can be maintained and the occurrence of phenomena such as whitening of the film can be reduced, so it 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). In this range, the effect of improving the exposure sensitivity and the chemical resistance of the cured film becomes easy to obtain.

The photosensitive resin composition of the present invention may also contain an antioxidant. By containing antioxidants, the yellowing of the cured film and the decrease in mechanical properties such as elongation during the subsequent heat treatment can be suppressed. In addition, it is preferable because it can inhibit oxidation of metal materials by its anti-rust effect on metal materials.

As the antioxidant, a hindered phenol antioxidant or a hindered amine antioxidant is preferred. In addition, the number of phenol groups or amine groups in one molecule is preferably 2 or more, and more preferably 4 or more in order to easily obtain the antioxidant effect.

Examples of the hindered phenol-based antioxidant include the following, but are not limited to the following structures.

Hindered phenol antioxidants inhibit the diffusion of free radicals and therefore also have the effect of improving resolution. Furthermore, when it can be developed with an alkali aqueous solution, it functions as a dissolution accelerator and also has the effect of suppressing residues.

Examples of hindered amine antioxidants include malonate bis(1,2,2,6,6-pentamethyl-4-piperidine) [[3,5-bis(1,1-dimethyl Ethyl)-4-hydroxyphenyl]methyl]butyl ester, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1 sebacate ,2,2,6,6-pentamethyl-4-piperidine ester, 1,2,2,6,6-pentamethyl-4-piperidine methacrylate, 2,2,6,6- Tetramethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, 1,1 -Reaction product of dimethylethyl hydroperoxide and octane, 4(1,2,2,6,6-pentamethyl-4-pyridine)butane-1,2,3,4-tetracarboxylic acid Ester or 4(2,2,6,6-tetramethyl-4-pyridine)butane-1,2,3,4-tetracarboxylate.

Examples of other antioxidants include: phenol, catechol, resorcinol, hydroquinone, 4-tertiary butylcatechol, 2,6-bis(tertiary butyl)p-cresol, phenol thiophene , 4-methoxyphenol. The addition amount of the antioxidant is preferably 0.1 to 10.0 parts by mass relative to 100 parts by mass of the resin (A), more preferably 0.3 to 5.0 parts by mass. Within this range, developability and the effect of suppressing discoloration due to heat treatment can be appropriately maintained.

The photosensitive resin composition of the present invention may also have a heterocyclic compound containing a nitrogen atom. By having a heterocyclic compound containing nitrogen atoms, high adhesion can be obtained in the bottom layer of metals that are easily oxidized, such as copper, aluminum, and silver. The mechanism is not clear yet, but it is speculated that it interacts with the metal surface through the metal coordination energy of the nitrogen atom, and that the interaction is stabilized by the large size of the heterocyclic ring.

Examples of heterocyclic compounds containing nitrogen atoms include: imidazole, pyrazole, indazole, carbazole, pyrazoline, pyrazoline, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyridine, ,three , cyanuric acid, isocyanuric acid and their derivatives.

More specifically, heterocyclic compounds containing nitrogen atoms include 1H-imidazole, 1H-benzimidazole, 1H-pyrazole, indazole, 9H-carbazole, 1-pyrazoline, and 2-pyrazole. Phine, 3-pyrazoline, pyrazoline, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tertiary butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole Azole, 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-tertiary butyl-2-hydroxyphenyl)benzotriazole, 2-(3-triazole Grade butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl) benzotriazole, 2-(2 '-Hydroxy-5'-tertiary 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, pyridine ,1,3,5-three , melamine, 2,4,6-tris(2-pyridyl)-1,3,5-tris , 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-tri , 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tri , 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tri -2-yl)-5-hydroxyphenyl, ginseng((meth)acryloyloxyethyl)trimer, glycidoxyethyl(glycidoxyethyl)trimer, etc. .

Among these, from the viewpoints of ease of synthesis, reactivity with metals, etc., 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, and 5-methyl -1H-methylbenzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-benzotriazole Base-1H-tetrazole, etc.

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

The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N- Dimethylacetamide, dimethyltrisoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylurea, N,N-dimethylisobutyric acid Polar aprotic solvents for amines, methoxy-N,N-dimethylpropylamine, etc.; tetrahydrofuran, dimethylpropylamine, etc. Ethers such as alkane, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone; ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol Esters such as monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol Alcohols such as toluene and xylene, etc.; aromatic hydrocarbons such as toluene and xylene. Two or more of these may be included.

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

The photosensitive resin composition of the present invention may also include surfactants; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; and alcohols such as ethanol for the purpose of improving wettability with the substrate. Ketones such as cyclohexanone, methyl isobutyl ketone, etc.; tetrahydrofuran, dihydrofuran Alkanes and other ethers.

In addition, in order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent as the silicon component within a range that does not impair storage stability. Examples of the silane coupling agent include trimethoxyaminepropylsilane, trimethoxycyclohexylepoxyethylsilane, trimethoxyvinylsilane, trimethoxymercaptanpropylsilane, and trimethoxyepoxypropylsilane. Oxypropylsilane, trimethoxysilylpropyl isocyanate, triethoxyaminepropylsilane, triethoxycyclohexylepoxyethylsilane, triethoxyvinylsilane, triethoxypropylsilane Ethoxymercaptan propylsilane, triethoxyglycidoxypropyloxypropylsilane, triethoxysilylpropyltriisocyanate, and trimethoxyaminepropylsilane or triethoxy Reaction product of aminopropylsilane and acid anhydride. This reactant can be used in the state of amide acid or in the state of imidization. Examples of acid anhydrides that undergo the reaction include: succinic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'- Biphenyl tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)terebic dianhydride, 4,4'-oxydiphthalein Acid dianhydride. The preferred content of the silane coupling agent is 0.01 to 10 parts by mass relative to 100 parts by mass of the resin (A).

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

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

Moreover, the photosensitive sheet of the present invention refers to a sheet that is not completely cured by applying the photosensitive resin composition of the present invention on a support and drying it at a temperature and time within a range that volatilizes the solvent. , which is soluble in organic solvents or alkaline aqueous solutions.

The support is not particularly limited, and various generally commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The joint surface between the support and the photosensitive resin composition may be surface treated with polysiloxane, silane coupling agent, aluminum chelating agent, polyurea, etc. in order to improve the adhesion and peelability. In addition, the thickness of the support is not particularly limited, but from the viewpoint of workability, the thickness is preferably in the range of 10 to 100 μm. Furthermore, in order to protect the film surface of the applied photosensitive composition, a protective film may be provided on the film surface. Thereby, the surface of the photosensitive resin composition can be protected from contaminants such as impurities and debris in the atmosphere.

Examples of methods for applying the photosensitive resin composition to the support include spin coating using a spin coater, spray coating, roller coating, screen printing, blade coater, die coater, calender coater, meniscus coater Coater, rod coater, roller coater, intermittent roller coater, gravure coater, screen coater, slot die coater and other methods. In addition, the coating film thickness varies depending on the coating method, the solid content concentration and viscosity of the composition, etc., but generally from the viewpoint of coating film uniformity, etc., the film thickness after drying is preferably 0.5 μm or more and 100 μm or less. .

Drying can use oven, heating plate, infrared, etc. The drying temperature and drying time may be within a range that can volatilize the solvent, and are preferably appropriately set in a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, it is preferable to carry out the reaction in the range of 40°C to 150°C for 1 minute to several tens of minutes. Moreover, these temperatures may be combined and the temperature may be raised stepwise. For example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

Next, a method of 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 aforementioned photosensitive sheet is laminated on the substrate. As the substrate, a metal-plated copper substrate or a silicon wafer can be used; and as the material, ceramics, gallium arsenide, etc. can be used, but are not limited to these. As the coating method, there are methods such as spin coating using a spin coater, spray coating, and roller coating. In addition, the coating film thickness varies depending on the coating technique, the solid content concentration and viscosity of the composition, but is usually applied so that the film thickness after drying becomes 0.1 to 150 μm.

In order to improve the adhesion between the substrate and the photosensitive resin composition, the substrate may also be pre-treated with the aforementioned silane coupling agent. For example, the silane coupling agent is prepared by dissolving 0.5 to 0.5% of the silane coupling agent in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. 20 mass% solution. Then, the prepared solution is subjected to surface treatment on the substrate by spin coating, dipping, spray coating, steam treatment, etc. Depending on the situation, heat treatment at 50°C to 300°C is then performed to allow the reaction between the substrate and the silane coupling agent to proceed.

Next, the substrate coated with the photosensitive resin composition or the substrate on which the photosensitive sheet of the present invention is laminated is dried to obtain a photosensitive resin film. Drying is preferably carried out in the range of 50°C to 150°C for 1 minute to several hours using an oven, a hot plate, infrared rays, or the like. In addition, the photosensitive sheet does not necessarily need to undergo a drying step.

Next, the photosensitive resin film is irradiated with chemical rays through a mask having a desired pattern to perform exposure. As chemical rays used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i-rays (365nm), h-rays (405nm), and g-rays (436nm) of a mercury lamp are preferably used.

Then, the exposed photosensitive resin film can also be subjected to a post-exposure baking (PEB) step according to requirements. The PEB step is preferably performed in the range of 50°C to 150°C for 1 minute to several hours using an oven, a hot plate, infrared rays, etc.

In order to form the pattern of the resin, a developer is used after exposure 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 insoluble in an alkali aqueous solution, preferred solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, and N,N-dimethylethyl Amide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. As the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferred. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Moreover, two or more types of each solvent may be used, for example, several types may be combined.

On the other hand, in the case of a photosensitive resin composition dissolved in an alkali aqueous solution, the developer used for development is one that dissolves and removes the alkali aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkali compound is dissolved. Examples of the alkali compound include: tetramethylammonium hydroxide, diethanolamine, diethylamine ethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, and dimethylamine , dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. In addition, depending on the situation, these alkali aqueous solutions may contain N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylformamide alone. Polar solvents such as methyl styrene, γ-butyrolactone, dimethylacrylamide, etc.; alcohols such as methanol, ethanol, isopropanol, etc.; esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc.; cyclic Ketones such as pentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc., or a combination of several thereof. After development, it is preferred to rinse with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developer, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. can also be used. When using water, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate can also be added to the water and then rinsed.

After development, a temperature of 150°C to 350°C is applied to proceed the thermal cross-linking reaction to harden it. This heat treatment selects a certain temperature and performs stepwise temperature increase, or selects a certain temperature range and performs continuous temperature increase, and is carried out for 5 minutes to 5 hours. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes respectively. The lower limit of the hardening conditions in the present invention is preferably 170°C or higher, but in order to fully advance hardening, the lower limit is more preferably 180°C or higher. In addition, the upper limit of the hardening conditions is not particularly limited, but from the viewpoint of suppressing film shrinkage and stress, it is preferably 280°C or lower. Moreover, since this invention provides the cured film which is excellent in low-temperature curability especially, it is more preferable that it is 250 degreeC or less, and it is more preferable that it is 230 degreeC or less.

The 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 can be suitably used as a passivation film of a semiconductor, a surface protective film of a semiconductor element, an interlayer insulating film, an interlayer insulating film in a multilayer wiring for high-density mounting of 2 to 10 layers, and an insulating layer of an organic electroluminescent element. etc., but are not limited to these, and may adopt various structures. In addition, the substrate surface on which the cured film is formed can be appropriately selected according to the use and procedure, and examples thereof include silicon, ceramics, metal, epoxy resin, etc. The substrate surface may also be a substrate composed of two or more of these materials.

Next, an application example of a semiconductor device having a bump using a cured film obtained by curing the photosensitive resin composition of the present invention will be described using drawings. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps according to the present invention. As shown in FIG. 1 , on a silicon wafer 1 , a passivation film 3 is formed on an input-output aluminum (hereinafter abbreviated as Al) pad 2 , and a through hole is formed in the passivation film 3 . An insulating film 4 is formed thereon by forming a pattern of a cured film cured by curing the photosensitive resin composition of the present invention, and a metal (Cr, Ti, etc.) film 5 is formed in connection with the Al pad 2 , and electrolytic plating is used. Metal wiring (Al, Cu, etc.) 6 is formed. The metal film 5 is etched around the solder bump 10 to insulate each pad. Barrier metal 8 and solder bumps 10 are formed on the insulated pad. The cured film formed by curing the photosensitive resin composition of the insulating film 7 can be processed into a thick film in the dicing lane 9 .

In addition, when a polyimide-based resin is used for the cured film of the present invention, it has excellent breaking point elongation and breaking point strength, and can relax the stress from the sealing resin during installation, thereby preventing the low-k layer from being damage, and can provide a highly reliable semiconductor device.

Next, a detailed manufacturing method of the semiconductor device is described in FIG. 2 . As shown in 2a of FIG. 2 , an input/output Al pad 2 is formed on a silicon wafer 1 , a passivation film 3 is formed, and a pattern of a cured film cured by curing the photosensitive resin composition of the present invention is formed to form an insulating film. 4. Next, as shown in 2b of FIG. 2 , a metal (Cr, Ti, etc.) film 5 is formed to connect to the Al pad 2 . As shown in 2c of FIG. 2 , a metal wiring 6 is formed by electroplating. Next, as shown in 2d' of FIG. 2 , the photosensitive resin composition before curing of the present invention is applied, and a photoetching step is performed to form a pattern as shown in 2d of FIG. 2 to form an insulating film 7 . At this time, the photosensitive resin composition before curing of the insulating film 7 is processed into a thick film in the dicing lane 9 . If the target thickness cannot be achieved with one coating, it can be coated multiple times. When forming a multi-layer wiring structure with three or more layers, the above steps can be repeated to form each layer.

Next, as shown in 2e and 2f of FIG. 2 , the barrier metal 8 and the solder bump 10 are formed. Then, cutting is performed along the final cutting lane 9, and each wafer is cut and separated. If the insulating film 7 is not patterned in the dicing lane 9 or if residue remains, cracks etc. may occur during dicing, thereby affecting the reliability evaluation of the wafer. Therefore, the present invention can provide pattern processing excellent in thick film processing, and is excellent in achieving high reliability of semiconductor devices. [Example]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each Example and Comparative Example will be described. The evaluation system used an uncured photosensitive resin composition (hereinafter referred to as varnish) filtered in advance through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore diameter of 1 μm.

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

(2) Pattern processability (2)-1 Sensitivity A The varnish using polyimide-based resin and epoxy resin obtained in each example and comparative example was spin-coated on the silicon wafer using a spin coater (1H-360S manufactured by MIKASA Co., Ltd.), and then a hot plate (Dainippon Co., Ltd. SCW-636 manufactured by SCREEN Co., Ltd. was pre-baked at 120°C for 3 minutes to produce a pre-baked film with a film thickness of 11 μm. For the obtained prebaked film, a parallel light mask alignment exposure machine (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Co., Ltd.) was used, and an ultrahigh-pressure mercury lamp was used as a light source (g-ray, h-ray, i-ray). Mixed rays), through the grayscale mask for sensitivity measurement (2~50μm pattern with 1:1 lines and spacing. The transmittance is 1%, 5%, 10%, 12%, 14% respectively , 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50% and 60% of the area.) for contact exposure. Then, if the varnish is a negative type, it is exposed and baked for 1 minute at 120°C, and then developed using a coating and developing device MARK-7. If the polymer is not soluble in alkali aqueous solution, use cyclopentanone as the developer, rinse and develop for 2 minutes, and then rinse with propylene glycol monomethyl ether acetate for 30 seconds. When the polymer is dissolved in an alkali aqueous solution, 2.38% by mass tetramethylammonium hydroxide (hereinafter abbreviated as "TMAH") aqueous solution (trade name "ELM-D", manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used as a developer and immersed Develop for 90 seconds, then rinse with water for 30 seconds.

After development, the film thickness is measured, and the minimum exposure level at which the remaining film rate in the exposed area exceeds 90% is used as the sensitivity. Exposure is measured with an I-ray illuminance meter. In addition, the film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd. with a refractive index of 1.629. The film thickness described below is also the same.

(2)-2 Sensitivity B Use a spin coater to spin-coat the varnish using the polysiloxane obtained in each example and comparative example on a ^10x10cm2 alkali-free glass substrate. Use a heating plate to preheat at 90°C. Bake for 2 minutes to make a pre-baked film with a film thickness of 2 μm.

For the pre-baked film produced, PLA-501F was used, an ultra-high-pressure mercury lamp was used as the light source (a mixed ray of g-ray, h-ray, and i-ray), and a gray-scale mask (2 to 50 μm) was used for sensitivity measurement. 1:1 line & spacing pattern. The penetration rates are 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35 respectively %, 40%, 50% and 60% of the area.) for contact exposure. Thereafter, an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.) was used, using 0.045 mass% potassium hydroxide aqueous solution or 2.38 mass% TMAH, rinse development for 100 seconds, and then rinsed with water for 30 seconds. . After development, the film thickness is measured, and the minimum exposure level at which the remaining film rate in the exposed area exceeds 90% is used as the sensitivity. Exposure is measured with an I-ray illuminance meter. In addition, the film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd. with a refractive index of 1.550. The film thickness described below is also the same.

(2)-3Developability A Measure the minimum pattern size after development at the exposure of sensitivity A defined by (2)-1.

(2)-4Developability B Measure the minimum pattern size after development at the exposure of sensitivity B defined in (2)-2.

(3) Evaluation of chemical resistance (3)-1 Chemical resistance evaluation A Using a coating and developing device MARK-7, the polyimide-based resin and epoxy resin obtained from each example and comparative example were spin-coated. The resin varnish is applied on the silicon wafer so that the film thickness becomes 10 μm after pre-baking at 120°C for 3 minutes. After pre-baking, in the case of negative type, use PLA-501F and apply it at 300 mJ/cm ^2. Expose the entire surface. In the case of positive type, use the inert oven CLH-21CD-S directly. Under nitrogen flow, increase the temperature to 180°C with an oxygen concentration of 20 ppm or less and a heating rate of 3.5°C per minute, and perform heat treatment at each temperature. 1 hour. When the temperature becomes 50°C or lower, the silicon wafer is taken out, the cured film is immersed in an organic chemical solution (dimethylsulfoxide: 25 mass% TMAH aqueous solution = 92:2) at 40°C for 10 minutes, and the peeling of the pattern and film thickness are observed. Change (indicating swelling or dissolution amount). As a result, the pattern was evaluated as 4 when the pattern did not peel off and the film thickness changed by 5% or less; the pattern did not peel off and the film thickness changed by more than 5% and the film thickness changed by 10% or less as 3; the pattern did not peel off and the film thickness changed by more than 10%. % and less than 30% is evaluated as 2, and the case where the pattern is peeled off without remaining film or the film thickness change exceeds 30% is evaluated as 1. The one with no peeling pattern and smaller change in film thickness has better chemical resistance.

(3)-2 Chemical resistance evaluation B The varnish using polysiloxane obtained from each Example and Comparative Example was spin-coated on a glass substrate with ITO sputtered on the surface (hereinafter referred to as "ITO substrate") using a spin coater, using a hot plate (trade name: SCW -636, manufactured by Dainippon Screen Manufacturing Co., Ltd.) and prebaked at 100°C for 2 minutes to produce a film with a film thickness of 2.0 μm.

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

The obtained cured film was immersed in photoresist stripping liquid N300 at 50° C. for 3 minutes, and the peeling of the pattern and the change in film thickness (indicating the amount of swelling or elution) were observed. The evaluation of the results was performed in the same manner as the aforementioned (3)-1 chemical resistance evaluation A.

(4) Measurement of breaking point elongation and breaking point strength. Use the coating and developing device ACT-8 to spin-coat the varnish using polyimide and epoxy resin obtained from each example and comparative example at 120 After prebaking at ℃ for 3 minutes, the film thickness becomes 11μm. After coating on a 6-inch silicon wafer and prebaking, in the case of negative type, use PLA and expose the entire surface at 300mJ/cm ² , in the case of positive type, use the inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) directly, raise the temperature to 180°C at an oxygen concentration of 20 ppm or less at 3.5°C/min, and perform heat treatment at each temperature for 1 hour. . When the temperature becomes 50° C. or lower, the silicon wafer is taken out and immersed in 45 mass % hydrofluoric acid for 5 minutes to peel the cured film of the resin composition from the wafer. This film was cut into a rectangle with a width of 1.5 cm and a length of 9 cm, and stretched using a tension machine RTM-100 (manufactured by ORIENTEC Co., Ltd.) at a room temperature of 23.0°C and a humidity of 45.0% RH at a stretching speed of 50 mm/min. (Chuck distance = 2cm), measure the elongation at break point (%) and strength at break point (MPa). The measurement system is to conduct 10 rectangular slices per specimen, and calculate the average of the first five points with higher values from the results (significant figures = 2 digits). This evaluation was performed as a mechanical property evaluation of polyimide and epoxy resin.

(5) Evaluation of copper substrate adhesion (5)-1 Copper substrate adhesion evaluation A The following method was used to evaluate the adhesion to metallic copper.

First, varnish is applied on a metal-plated copper substrate with a thickness of about 3 μm by spin coating, and then a hot plate (D-SPIN manufactured by Dainippon Screen Manufacturing Co., Ltd.) is used to bake it at 120°C for 3 minutes to create the final product. Pre-baked film with a thickness of 8μm. In the case of the negative type, use PLA to expose the entire surface at 300mJ/ ^cm2 . In the case of the positive type, use an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) directly, with an oxygen concentration of 20 ppm or less, and 3.5°C. /min to 230°C, and heat-treat the film at 230°C for 1 hour. When the temperature becomes 50° C. or lower, the substrate is taken out and divided into two. For each substrate, a single-sided knife is used to score 10 rows and 10 columns of checkerboard-shaped scratches at 2 mm intervals on the cured film. Using one of the sample substrates, it was peeled with "cellotape" (registered trademark), and the adhesion characteristics between the metal material/resin cured film were evaluated so that a few of the 100 strips peeled off. In addition, another sample substrate was subjected to PCT treatment for 400 hours using a fracturing test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai ESPEC Co., Ltd.) under saturated conditions of 121°C and 2 atmospheres, and then the above-mentioned tear test. For any substrate, in the tear test, the number of peels is 0 as 5, more than 1 and less than 10 peels as 4, 10 or more and less than 30 as 3, 30 as More than 50 and less than 50 are rated as 2, and more than 50 are rated as 1.

The smaller the number of peelings, the better the adhesion.

(5)-2 Copper substrate adhesion evaluation B On the copper substrate, a cured film having a film thickness of 2.0 μm was formed in the same manner as the method described in (3)-2 above. The obtained substrate was divided into two, and for each substrate, a single-sided knife was used to score 10 rows and 10 columns of checkerboard-shaped scratches at 2 mm intervals on the hardened film. Using one of the sample substrates, it was peeled off with "Celluloid Tape" (registered trademark) and peeled off a few squares out of 100 to evaluate the adhesion characteristics between the metal material/resin cured film. In addition, for another sample substrate, a pressure cracking test (PCT) device (HAST CHAMBER EHS-211MD manufactured by Tabai ESPEC Co., Ltd.) was used to perform PCT treatment at 85°C and 85% for 25 hours, and then the above-mentioned tear test was performed. . The determination of adhesion was performed in the same manner as the above-mentioned (5)-1 Copper substrate adhesion evaluation A.

(6) Measurement of imidization rate The imidization rate (%) of the cured film can be easily determined by the following method. Proceed to the heat treatment in the same procedure as (4) to form a cured film on the silicon wafer. Next, the infrared absorption spectrum of the produced cured film was measured (based on the silicon wafer), and the presence of the absorption peak (near 1780 cm ^-1 , near 1377 cm ^-1 ) due to the amide imine structure of the polyimide was confirmed. Find the peak intensity (X) near 1377cm ^-1 . Next, the cured film was heat-treated at 350° C. for 1 hour, and an infrared absorption spectrum was measured to determine the peak intensity (Y) near 1377 cm ⁻¹ . These peak intensity ratios correspond to the content of the acyl imine group in the polymer before heat treatment, that is, to the acyl imidization rate (the acyl imidization rate = X/Y × 100 (%)).

(7) Storage stability of varnish Measure the viscosity of the prepared varnish and the viscosity after being placed at 23°C for 2 weeks, and calculate the change rate of the viscosity before and after being placed.

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

(8)Hardness On the ITO substrate, a cured film having a film thickness of 2.0 μm was formed in the same manner as the method described in (3)-2 above. The pencil hardness of the obtained cured film was measured based on JIS "K5600-5-4 (date of establishment = 1999/04/20)". This evaluation was performed as a mechanical property evaluation of polysiloxane.

(9) Coefficient of thermal expansion (CTE) A self-standing film of the cured film was produced in the same procedure as (4). The film was cut into 3.0cm×0.5cm with a single-sided knife, and a differential scanning calorimeter (manufactured by SEIKO INSTRUMENTS) was used. , TMA/SS6100), under nitrogen flow, under the condition of 80mL/min, at a speed of 10℃/min, the temperature was increased from 25℃ to 400℃ for measurement. The linear expansion coefficient from 50°C to 150°C was calculated as CTE (10 ^-6 /K).

[Synthesis Example 1: Synthesis of polyimide precursor (P-1)] Put 31.02g (0.10mol) of 4,4'-oxydiphthalic dianhydride (ODPA) into a detachable flask with a capacity of 500ml, and put 26.03g (0.20mol) of methacrylic acid 2 at room temperature. -Hydroxyethyl ester (HEMA) and 76 ml of γ-butyrolactone, while stirring, add 16.22 g (0.21 mol) of pyridine to obtain a reaction mixture. After the heat generated by the reaction ends, the mixture is allowed to cool to room temperature and left for another 16 hours.

Then, 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, and then stirred for 18.62 g (0.093 mol) of 4,4'-diaminodiphenyl ether (DAE) was added in 5 portions over 20 minutes. After stirring at room temperature for 2 hours, 6 ml of ethanol (EtOH) was added and stirred for 1 hour, and then 65 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture is removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 800 ml of EtOH to produce a precipitate containing crude polymer. The resulting crude polymer was filtered out 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. The precipitate was collected by filtration, washed with water three times, and then dried under vacuum to obtain a powdery polyimide precursor (P-1). The molecular weight of the polyimide precursor (P-1) was measured with a gel permeation chromatography analyzer (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 31,000 and the PDI was 2.6. The polyimide precursor (P-1) is insoluble in an aqueous alkali solution, and the photosensitive resin composition using the precursor 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. Here, 96.72g (0.16 mole) of the diamine (HA) of the following structure and 4.97g (0.02 mole) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) was added together with 100 g of NMP, and 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-aminephenol (MAP) was added as a blocking agent 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 dropped over 10 minutes. After dropping, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then the solution was poured into 1 L of water to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80° C. for 20 hours to obtain a powder of polyimide precursor resin (P-2). The molecular weight of the polyimide precursor (P-1) was measured with a gel permeation chromatography analyzer (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 25,000 and the PDI was 2.3. The polyimide precursor (P-2) is soluble in an alkali aqueous solution, and the photosensitive resin composition using the polyimide precursor (P-2) is developed with a 2.38 mass% TMAH aqueous solution.

[Synthesis Example 3: Synthesis of polyimide precursor (P-3)] Except having used 29.42g of biphenyltetracarboxylic anhydride (BPDA) instead of ODPA, it carried out similarly to Synthesis Example 1, and obtained the polyimide precursor (P-3). The Mw of the polyimide precursor (P-3) is 34000 and the PDI is 2.5. The polyimide precursor (P-3) was developed with cyclopentanone.

[Synthesis Example 4: Synthesis of polyimide precursor (P-4)] 18.03g (0.090mol) of DAE and 0.80g (0.002mol) of 1,3,5-paraben(4-aminophenoxy)benzene (TAPOB) were used instead of 18.62g of DAE. In addition, the synthesis was carried out Example 1 was carried out in the same manner to obtain a polyimide precursor (P-4). The Mw of the polyimide precursor (P-4) is 27000 and the PDI is 2.9. The polyimide precursor (P-4) was developed with cyclopentanone.

[Synthesis Example 5: Synthesis of polysiloxane (P-5) solution] In a 500ml three-neck flask, feed 43.74g (0.195mol) of p-styryltrimethoxysilane (St) and 14.06g (0.06mol) of γ-acrylylpropyltrimethoxysilane (Acry) , 11.80g (0.045mol) 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.173g TBC, 74.58g PGME, and add 0.348g phosphoric acid (relative to A phosphoric acid aqueous solution dissolved in 17.01g of water (the feed monomer is 0.50% by mass). Thereafter, the three-necked flask was immersed in a 70°C oil bath and stirred for 90 minutes, and then the oil bath was heated to 115°C over 30 minutes. One hour after the temperature rise started, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and heating and stirring were started for 2 hours (the internal temperature was 100 to 110°C) to obtain a polysiloxane solution. In addition, nitrogen gas was flowed in at 0.05 liter/minute while the temperature was raised and heated and stirred. During the reaction, a total of 36.90 g of by-products methanol and water were distilled off. PGME was added to the obtained polysiloxane solution so that the solid content concentration became 40 mass %, and a polysiloxane (P-5) solution was obtained.

[Synthesis Example 6: Synthesis of polysiloxane (P-6) solution] In a 500ml three-neck flask, feed 44.86g (0.200mol) p-styryltrimethoxysilane (St), 39.66g (0.200mol) phenyltrimethoxysilane (Ph), 6.81g (0.050 mol) of methyltrimethoxysilane (Me), 13.12g (0.050mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.522g of TBC, and 74.58g of PGME, while stirring at room temperature A phosphoric acid aqueous solution in which 0.448 g of phosphoric acid (0.50 mass % with respect to the feed monomer) was 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 oil bath was heated to 115°C over 30 minutes. One hour after the temperature rise started, the internal temperature (solution temperature) of the three-necked flask reached 100°C, and heating and stirring were started for 2 hours (the internal temperature was 100 to 110°C) to obtain a polysiloxane solution. In addition, nitrogen gas was flowed in at 0.05 liter/minute while the temperature was raised and heated and stirred. During the reaction, a total of 58.90 g of methanol and water were distilled off as by-products. To the obtained polysiloxane solution, PGME was added so that the solid content concentration became 40 mass %, and a polysiloxane (P-6) solution was obtained.

Table 1

The base generator used in Examples and Comparative Examples is shown below.

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

B-II: Guanidine 2-(3-benzylphenyl)propionate

B-III: Compounds with the following structure

B-IV: Compounds with the following structure

B-V: Compounds with the following structure

B-VI: Compounds with the following structure

B-VII: Compounds with the following structure

B-VIII: Compounds with the following structure

B-IX: Compounds with the following structure

B-X: N-tertiary butoxycarbonyldimethylpiperidine

[Example 1] Under a yellow light, 10.00g of polyimide precursor (P-1), 0.50g of 1,2-octanedione, 1-[4-(phenylthio)-2-(o-phenyl) Oxime)] ("Irgacure OXE-01 (trade name)" manufactured by BASF), 0.30 g of B-I, 2.00 g of NKESTER 4G (trade name) (made by Shin-Nakamura Chemical Industry Co., Ltd., chemical name: tetraethylene glycol dimethacrylate), 0.2g of N-phenyldiethanolamine, and 0.30g of 3-trimethoxysilylphthalamide were dissolved in 15.15g of N-methylpyrrolidone (NMP) and 3.81g of To ethyl lactate (EL), 0.10 g of a 1 mass % EL solution of "Polyflow 77 (trade name)" (manufactured by Kyoei Chemical Co., Ltd.) which is an acrylic surfactant was added and stirred to obtain a varnish. According to the above evaluation method, the characteristics of the obtained varnish were measured: pattern processability (sensitivity A, developability A), chemical resistance A, elongation at breaking point, strength at breaking point, thermal expansion coefficient, and copper substrate adhesion evaluation A , acyl imidization rate measurement and storage stability. [Example 2] The procedure was carried out in the same manner as in Example 1 except that B-I was changed to B-II. [Example 3] The procedure was carried out in the same manner as in Example 1 except that B-I was changed to B-III. [Example 4] The procedure was carried out in the same manner as in Example 1 except that B-I was changed to B-IV. [Example 5] The procedure was carried out in the same manner as in Example 1 except that B-I was changed to B-V. [Example 6] The procedure was carried out in the same manner as in Example 1 except that B-I was changed to B-VI.

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

[Example 12] The procedure was carried out in the same manner as Example 3 except that the addition amount of B-III was 0.01 g. [Example 13] The procedure was carried out in the same manner as Example 3 except that the amount of B-III added was 0.03 g. [Example 14] The procedure was carried out in the same manner as Example 3 except that the amount of B-III added was 0.7 g. [Example 15] The procedure was carried out in the same manner as in Example 3 except that the addition amount of B-III was 1.0 g. [Example 16] The procedure was carried out in the same manner as in Example 3 except that the addition amount of B-III was 2.0 g. [Example 17] Under a yellow light, 10.00 g of polyimide precursor (P-1), 0.80 g of 2-(dimethylamino)-2-[(4-methylphenyl)methyl base]-1-[4-(4- Phylyl)phenyl]-1-butanone ("Irgacure 379 (trade name)" manufactured by BASF), 0.2 g of diethyl 9-oxosulfide , 0.30g of B-III, 2.00g of 4G, 0.2g of N-phenyldiethanolamine, and 0.30g of 3-trimethoxysilylphthalamide were dissolved in 15.15g of NMP and 3.81g of EL, and added 0.10 g of a 1 mass% EL solution of Polyflow 77 was stirred to obtain a varnish. Regarding the properties of the obtained varnish, the pattern processability (sensitivity A, developability A), chemical resistance A, breaking point elongation, breaking point strength, thermal expansion coefficient, and copper substrate adhesion evaluation A were measured using the above evaluation methods. , acyl imidization rate measurement and storage stability.

[Example 18] The procedure was carried out in the same manner as in Example 17, except that Irgacure 379 was changed to bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide ("Irgacure 819 (trade name)" manufactured by BASF). . [Example 19] Change Irgacure379 to 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propyl)-benzyl]phenyl}-2-methyl-propan-1-one (" Except for Irgacure 127 (trade name, "BASF"), it was carried out in the same manner as in Example 17. [Example 20] The procedure was carried out in the same manner as in Example 17, except that Irgacure 379 was changed to p-dimethylamine benzoate ethyl ester. [Example 21] The procedure was carried out in the same manner as in Example 17 except that Irgacure379 was changed to 4-phenylbenzophenone. [Example 22] A solid polyfunctional aromatic epoxy resin (YDCN-700-10 (trade name), manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) that is a cresol novolak type multifunctional epoxy resin was used instead of the polyimide precursor (P- 1) The same procedure as in Example 1 was performed except that 2 g of dipenterythritol hexaacrylate (DPHA (trade name), manufactured by Nippon Kayaku Co., Ltd.) was added. Only the imidization rate was not measured.

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

[Example 37] Under a yellow light, make 0.080g of ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyl) base oxime) ("Irgacure" (registered trademark) OXE-02 (trade name), manufactured by BASF Japan Co., Ltd.) and 0.160 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine Oxide ("Irgacure" (registered trademark)-819 (trade name), manufactured by BASF Japan Co., Ltd.), 0.200 g of ethylene bis(oxyethylene)bis[3-(5-tertiary butyl-4-hydroxy - m-tolyl)propionate] ("IRGANOX" (registered trademark)-245 (trade name), BASF Japan Co., Ltd.) PGME 10% by mass solution, 0.800 g of neopentyl acrylate ("Light Acrylate" "(registered trademark) PE-3A (trade name), manufactured by Kyeisha Chemical Co., Ltd.), 0.16g of B-I, 0.120g of 3-methacryloxypropyltrimethoxysilane (KBM-503( Trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in a mixed solvent of 8.615g PGME and 3.200g PGMEA, and a polysiloxane-based surfactant (trade name “BYK” (registered trademark)-333, BYK・Japan) was added 0.020 g (equivalent to a concentration of 100 ppm) of a 10% by mass PGME diluted solution manufactured by (Co., Ltd.) and stirred. Thereafter, 6.645 g of the polysiloxane (P-5) solution was added as (A) polysiloxane, and then filtered with a 0.45 μm filter to obtain a polysiloxane-containing varnish. The obtained varnish was evaluated for the sensitivity B, developability B, chemical resistance B, hardness, copper substrate adhesion B, and storage stability described above. [Example 38] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-II. [Example 39] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-III.

[Example 40] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-IV. [Example 41] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-V. [Example 42] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-VI. [Example 43] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-VII. [Example 44] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-VIII. [Example 45] The procedure was carried out in the same manner as in Example 37 except that B-I was changed to B-IX.

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

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

table 2-1

Table 2-2

table 3

Table 4

table 5

Table 6

Table 7

Table 8

Table 9

Table 10

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: Cutting lane 10: Solder bumps

FIG. 1 is an enlarged cross-sectional view showing a pad portion of a semiconductor device having bumps. FIG. 2 is a diagram showing a detailed manufacturing method of a semiconductor device having bumps.

without.

Claims (22)

A photosensitive resin composition containing (A) a resin containing a polyimide precursor having a biphenyl structure, (B) a thermal base generator and (C) a photosensitive agent, wherein the (B) The thermal base generator contains a guanidine derivative and/or a biguanide derivative having a quaternary boron anion, and the (C) photosensitizer contains (c-1) a photoacid generator and/or (c-2) a light free base polymerization initiator. A photosensitive resin composition containing (A) a resin containing polysiloxane having a styrene group, (B) a thermal base generator, and (C) a photosensitive agent, wherein the (B) ) The thermal base generator contains a guanidine derivative and/or a biguanide derivative, and the (C) photosensitizer contains (c-1) a photoacid generator and/or (c-2) a photoradical polymerization initiator. The photosensitive resin composition of claim 1, wherein the (A) resin further contains polyimide, polybenzo

Azole, polybenzo

Any one or more of the group of azole precursors and polysiloxanes. The photosensitive resin composition of claim 2, wherein the (A) resin further contains a polyimide precursor. The photosensitive resin composition of claim 1, wherein the (A) resin further contains polysiloxane. The photosensitive resin composition of claim 2, wherein the (B) thermal base generator includes a guanidine derivative and/or a biguanide derivative having a quaternary boron anion. The photosensitive resin composition of claim 1, wherein the (B) thermal base generator contains a compound represented by general formula (1);

(In the general formula (1), R ¹ to R ⁷ are each independently represented by a hydrogen atom or a substituted or unsubstituted alkyl group with 1 to 50 carbon atoms, an aryl group with 6 to 50 carbon atoms, or an alkyl group with 7 to 50 carbon atoms. Aralkyl, Z ^- represents the borate anion). The photosensitive resin composition of claim 2, wherein the (B) thermal base generator contains a compound represented by general formula (1);

(In the general formula (1), R ¹ to R ⁷ are each independently represented by a hydrogen atom or a substituted or unsubstituted alkyl group with 1 to 50 carbon atoms, an aryl group with 6 to 50 carbon atoms, or an alkyl group with 7 to 50 carbon atoms. Aralkyl, Z ^- represents carboxylate or borate anion). The photosensitive resin composition of claim 7, wherein ^Z- in the general formula (1) includes the structure of the general formula (4);

(In the general formula (4), R ²⁶ to R ²⁹ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group with 1 to 50 carbon atoms, an alkoxy group with 1 to 50 carbon atoms, or an alkoxy group with 2 to 50 carbon atoms. Alkenyl group, alkynyl group with 2 to 50 carbon atoms, aryl group with 6 to 50 carbon atoms, aralkyl group with 7 to 50 carbon atoms, arylalkynyl group with 7 to 50 carbon atoms, furyl group, thienyl group or pyrrolyl group ). The photosensitive resin composition of claim 8, wherein ^Z- in the general formula (1) includes any structure in the general formulas (2) to (4);

(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 with 1 to 50 carbon atoms, an aryl group with 6 to 50 carbon atoms, Aralkyl group with 7 to 50 carbon atoms or alkoxy group with 1 to 50 carbon atoms);

(In the 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 with 1 to 50 carbon atoms, an aryl group with 6 to 50 carbon atoms, Aralkyl group with 7 to 50 carbon atoms or alkoxy group with 1 to 50 carbon atoms, Y represents an oxygen atom or a sulfur atom);

(In the general formula (4), R ²⁶ to R ²⁹ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group with 1 to 50 carbon atoms, an alkoxy group with 1 to 50 carbon atoms, or an alkoxy group with 2 to 50 carbon atoms. Alkenyl group, alkynyl group with 2 to 50 carbon atoms, aryl group with 6 to 50 carbon atoms, aralkyl group with 7 to 50 carbon atoms, arylalkynyl group with 7 to 50 carbon atoms, furyl group, thienyl group or pyrrolyl group ). The photosensitive resin composition of claim 9 or 10, wherein Z ^- in the general formula (1) is the general formula (5);

(In the general formula (5), R ³⁰ represents 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. an alkynyl group, an aryl group with 6 to 14 carbon atoms, an aralkyl group with 7 to 15 carbon atoms, an arylalkynyl group with 7 to 15 carbon atoms, a furyl group, a thienyl group or a pyrrolyl group, and R ³¹ to R ³³ represent substituted or Unsubstituted aryl group with 6 to 50 carbon atoms). The photosensitive resin composition of claim 2, wherein the (A) resin further contains a polyimide precursor having a biphenyl structure. The photosensitive resin composition of claim 1, wherein the resin (A) contains a polyimide precursor having a residue of an amine compound having a valence of trivalent or higher. The photosensitive resin composition of claim 2, wherein the (A) resin further contains a polyimide precursor having a residue of an amine compound having a valence of trivalent or higher. The photosensitive resin composition of claim 1 or 2, wherein the (C) photosensitive agent contains (c-1) photoacid generator. The photosensitive resin composition of claim 1 or 2, wherein the (C) photosensitive agent contains (c-2) a photoradical polymerization initiator, and the (c-2) photoradical polymerization initiator contains a photoradical polymerization initiator selected from One or more of the group consisting of an alkylphenone compound, an aminobenzophenone compound, a diketone compound, a ketoester compound, a phosphine oxide compound, an oxime ester compound and a benzoate compound. The photosensitive resin composition of claim 1 or 2, wherein the content of the (B) thermal base generator is 0.1 to 10 parts by mass relative to 100 parts by mass of the resin (A). A photosensitive sheet formed of the photosensitive resin composition according to any one of claims 1 to 17. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 17 or the photosensitive sheet according to claim 18. A method for manufacturing a cured film, which includes applying the photosensitive resin composition according to any one of claims 1 to 17 on a substrate, or laminating and drying the photosensitive sheet according to claim 18 on the substrate. The steps of forming a photosensitive resin film; exposing the photosensitive resin film; developing the exposed photosensitive resin film; and subjecting the developed photosensitive resin film to heat treatment. The method for manufacturing a cured film according to Claim 20, wherein the step of heat-treating the developed photosensitive resin film includes a step of heat-treating at a temperature of 170° C. or more and 280° C. or less. An electronic component having a relief pattern of the cured film according to claim 19.