JP2006036949A - Aqueous alkali solution-soluble resin, composition including the same and hardened product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that has excellent photosensitivity to active energy ray, can form the patterns by developing with dilute alkali aqueous solution and is suitable as a solder mask ink of which the hardened membrane is highly insulative, has satisfactory flexibility, adhesiveness, gold plate resistance, electroless gold plating resistance and tin plating resistance. <P>SOLUTION: A diol compound (a) bearing an ethylenic unsaturated group in the molecule or the diol compound (a) and other diol compounds (d) are allowed to react with a polybasic acid anhydride (b) to form an ester compound (x), an epoxy compound (c) bearing two epoxy groups in the molecule is allowed to react with the carboxy groups in the ester compound (x). Further, the formed diol is allowed to react with polybasic acid anhydride (b') whereby alkali aqueous solution-soluble resin composition (A) is obtained. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous alkali-soluble resin, a composition containing the same, and a method for producing a cured product thereof. More specifically, the present invention relates to a solder mask for printed wiring (base) board, a solder mask for flexible printed wiring (base) board, and a multilayer print. Useful as interlayer insulation films for wiring (base) boards, photosensitive optical waveguides, photosensitive paint films, etc., developability, photosensitivity, flexibility, adhesion, solder heat resistance, chemical resistance, plating resistance, high insulation The present invention relates to a composition containing a specific resin that gives an excellent cured product, a method for producing the cured product, and a substrate having a layer of the cured product.

  Currently, some consumer printed wiring boards as well as most industrial printed wiring board solder masks use photolithography, that is, they are imaged by development after exposure, and further heat and / or light. It is the solder mask which uses the photocurable composition hardened | cured by irradiation. In consideration of environmental problems, an alkali development type solder mask composition using a dilute alkaline aqueous solution instead of an organic solvent as a developing solution has become mainstream. Examples of such an alkali development type solder mask composition using a dilute aqueous alkali solution include a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy resin and an unsaturated monobasic acid, and photopolymerization is initiated. A composition comprising an agent, a crosslinking agent, and an epoxy resin is known (for example, Patent Document 1). However, the cured product of this composition is hard, and when applied to a ball grid array (hereinafter referred to as BGA) substrate or a flexible substrate that is being used in many fields such as portable devices in recent years, the surface is cracked, This causes a problem that the bending cannot be followed.

As a material suitable for this BGA substrate and flexible substrate, a polybasic acid anhydride-modified epoxy acrylate resin obtained by reacting a polybasic acid anhydride with a reaction product of a polyfunctional bisphenol-based epoxy resin and (meth) acrylic acid is used. This composition is described in Patent Document 2. However, when this is used, although the crack resistance of the surface is improved, it is not sufficient in terms of photosensitivity and flexibility and cannot follow extreme bending.
In Patent Document 3, a polybasic compound is added to a urethane-modified vinyl ester resin comprising a vinyl ester resin obtained by reacting an epoxy compound having 1.2 or more epoxy groups in one molecule with an unsaturated monobasic acid. Although a photopolymerizable resin composition containing a urethane-modified acid-added vinyl ester resin obtained by adding an acid anhydride has been disclosed, the cured product can achieve performance that is almost satisfactory in flexibility, but is photosensitive. There were problems such as deterioration of heat resistance and insulation.

JP-A 61-243869 Japanese Patent No. 2868190 JP-A-9-52925

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speeds. As a result, the demand for solder masks has become increasingly sophisticated, and while maintaining more flexibility, There is a demand for improvement in electrical characteristics such as the property, gold plating resistance, electroless gold plating resistance, tin plating resistance, substrate adhesion, and high insulation. However, currently known solder masks cannot meet these requirements.
The object of the present invention is excellent in photosensitivity to active energy rays capable of drawing a fine image capable of corresponding to the high functionality of today's printed wiring boards, can be patterned by development with dilute alkaline aqueous solution, and post-cured (post-cured) Cured) The cured film obtained by thermosetting as the process has sufficient heat resistance and flexibility, and is suitable for solder mask ink with high insulation, adhesion, gold plating resistance, electroless gold plating resistance, and tin plating resistance. An object of the present invention is to provide an aqueous alkali-soluble resin that exhibits a composition and a cured product and their properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention.

That is, the present invention
(1) Polybasic acid anhydride (b) is added to diol compound (a) having an ethylenically unsaturated group in the molecule, or diol compound (d) other than diol compound (a) and compound (a). The carboxyl group of the ester compound (x) obtained by the reaction is reacted with an epoxy compound (c) having two epoxy groups in the molecule, and the resulting diol and polybasic acid anhydride (b ′) are reacted. An aqueous alkali-soluble resin (A) obtained by reacting;
(2) The diol compound (a) is a reaction product of an epoxy compound having two epoxy groups in the molecule and (meth) acrylic acid or cinnamic acid, and a polybasic acid anhydride is a dibasic acid monoanhydride And / or an alkaline aqueous solution-soluble resin (A) according to claim 1, which is a tribasic acid monoanhydride;
(3) Alkaline aqueous solution-soluble resin (A) as described in said (1) or (2) whose solid content acid value of alkali aqueous solution-soluble resin (A) is 30-150 mgKOH / g;

(4) 1. The alkaline aqueous solution-soluble resin (A) according to any one of (1) to (3) above,
2. Photopolymerization initiator (B),
3. Reactive crosslinking agent (C),
4). Curing component (D) as an optional component
A photosensitive resin composition comprising:
(5) A method for producing a cured product, wherein the photosensitive resin composition according to (4) is irradiated with active energy rays;
(6) A substrate having a layer of a cured product by the production method according to (5) above;
(7) An article having the substrate according to (6) above;

(8) A solder mask for a printed wiring board, a solder mask for a flexible printed wiring board, comprising the steps of applying the photopolymer composition according to claim 4, photocuring, alkali treatment and heat treatment, Production method of interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide or photosensitive paint film;
About.

  The alkaline aqueous solution-soluble resin (A) of the present invention includes a diol compound (a) having an ethylenically unsaturated group in the molecule, or a diol compound (d) other than the diol compound (a) and the compound (a), The carboxyl group of the ester compound (x) obtained by reacting the polybasic acid anhydride (b) is reacted with the epoxy compound (c) having two epoxy groups in the molecule, and the resulting diol and polybasic It is obtained by reacting with an acid anhydride (b ′), and is schematically represented by the following structural formula, for example.

However, the epoxy group of (c) reacts with the carboxyl group of (x) and (b ′) to form an ester bond. The photosensitive resin composition containing this resin is excellent in photosensitivity in forming a fine image corresponding to a high-performance printed wiring board by active energy rays such as ultraviolet rays, and can be patterned by development with a dilute aqueous alkali solution. In addition, the cured film obtained by heat curing in the post-curing (post-cure) process is flexible, adhesive, pencil hardness, solvent resistance, chemical resistance, acid resistance, heat resistance, gold plating resistance, electroless Gold plating resistance, tin plating resistance, high insulation, etc. are also fully satisfied, especially manufacturing of solder masks for flexible printed wiring boards, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides and photosensitive paint films, etc. Suitable for
In addition, by changing the charge ratio of the epoxy compound (c) and polybasic acid anhydride (b ′) and changing m + n and m in the above structural formula, the molecular weight and acid value of the resin contributing to various properties can be freely set. Can be controlled.

  The alkaline aqueous solution-soluble resin (A) of the present invention includes a diol compound (a) having an ethylenically unsaturated group in the molecule, or a diol compound (d) other than the diol compound (a) and the compound (a), Reaction of an epoxy compound (c) having two epoxy groups in the molecule with a carboxyl group of an ester compound (x) obtained by reacting the polybasic acid anhydride (b) (hereinafter referred to as the first reaction) (Hereinafter, referred to as a second reaction), and further obtained by reacting the produced diol with a polybasic acid anhydride (b ′) (hereinafter referred to as a third reaction).

  As the diol compound (a) having an ethylenically unsaturated group in the molecule used in the production of the aqueous alkali solution-soluble resin (A) of the present invention, reaction of dimethylolpropionic acid and 2-hydroxyethyl (meth) acrylate Product, reaction product of dimethylolpropionic acid and 2-hydroxypropyl (meth) acrylate, reaction product of dimethylolbutanoic acid and 2-hydroxyethyl (meth) acrylate, dimethylolbutanoic acid and 2-hydroxypropyl Reaction product of (meth) acrylate, reaction product of epoxy compound having two epoxy groups in molecule and (meth) acrylic acid or cinnamic acid, phenol compound having two phenolic hydroxyl groups in molecule And the reaction product of glycidyl (meth) acrylate and the like.

  Examples of the epoxy compound having two epoxy groups in the molecule include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F Type epoxy resin, bisphenol-S type epoxy resin, bisphenol type epoxy compound such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound; hydrogenation Bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3 -Of hexafluoropropane Hydrogenated bisphenol-type epoxy compounds such as poxy compounds; Halogenobisphenol-type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl ethers such as cyclohexanedimethanol diglycidyl ether Compound; Aliphatic diglycidyl ether compound such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether; Polysulfide type diglycidyl ether compound such as polysulfide diglycidyl ether; Biphenol type An epoxy resin etc. are mentioned.

  Examples of the phenol compound having two phenolic hydroxyl groups in the molecule include hydroquinone, catechol, resorcinol, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, Bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) Sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4- Hydroxyphenyl) di Tylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-) Chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethyl) Ruphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) Fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4′-biphenol And 3,3'-biphenol.

  The diol compound (a) is preferably a reaction product of an epoxy compound having two epoxy groups in the molecule and (meth) acrylic acid or cinnamic acid, and is a bisphenol-A type epoxy resin or bisphenol-F type epoxy resin. A reaction product of hydrogenated bisphenol-F type epoxy resin or hydrogenated bisphenol-A type epoxy resin and (meth) acrylic acid is particularly preferred.

  When the diol compound (d) is used in the production of the aqueous alkali solution-soluble resin (A) of the present invention, the diol compound (d) is different in two alcoholic hydroxyl groups other than the diol compound (a). Specific examples include aliphatic or alicyclic diol compounds bonded to carbon atoms. Specific examples include (poly) ethylene glycol, (poly) propylene glycol, trimethylene glycol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1 , 2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-dioe , Cyclohexane-1,2-dimethanol, cyclohexane-1,4-dimethanol, butadiene-acrylonitrile copolymer having a hydroxyl group at the terminal (for example, AT × 013 from Ube Industries), spiroglycol having a hydroxyl group at the terminal (for example, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.), dioxane glycol having a terminal hydroxyl group (for example, 2- ( 2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxy-1,3-dioxane, etc.), tricyclodecane-dimethanol having a hydroxyl group at the terminal, side chain of polystyrene having a hydroxyl group at the terminal (Eg, HS-6 manufactured by Toagosei Co., Ltd.) Diol compounds such as macromonomer having a rilonitrile copolymer in the side chain (for example, HN-6 manufactured by Toagosei Co., Ltd.), hydrogenated bisphenol-A, hydrogenated bisphenol-F, or these diol compounds and ethylene The reaction material with oxides, such as an oxide and a propylene oxide, etc. are mentioned.

  Although it does not specifically limit as polybasic acid anhydride (b) used for manufacture of aqueous alkali solution-soluble resin (A) of this invention, The dibasic acid 1 in which the dibasic acid forms the acid anhydride in a molecule | numerator 1 An anhydride, a tribasic acid monoanhydride in which any two carboxyl groups of a tribasic acid form an acid anhydride in the molecule, or a mixture of these acid monoanhydrides is preferred. Examples of the dibasic acid monoanhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Examples of the acid include succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Examples of the tribasic acid monoanhydride include trimellitic anhydride, tetrahydro trimellitic anhydride, and hexahydro trimellitic anhydride, with tetrahydro trimellitic anhydride being preferred.

In the first reaction, the diol compound (a) having an ethylenically unsaturated group in the molecule, or 1 equivalent of a hydroxyl group in the diol compound (d) other than the diol compound (a) and the compound (a), It is preferable to charge 0.5 to 3 equivalents, more preferably 0.8 to 1.2 equivalents of the polybasic acid anhydride (b). When this value is less than 0.5, the second reaction is difficult to proceed, and as a result, the overall molecular weight is lowered, and problems of photosensitivity and heat resistance are likely to occur. On the other hand, when this value exceeds 3, molecules are cross-linked during the second reaction and gelation is likely to occur.
As reaction temperature, it is 60-150 degreeC, for example, Preferably it is 80-120 degreeC. The reaction time is 2 to 10 hours, preferably 3 to 8 hours.

  Examples of the epoxy compound (c) having two epoxy groups in the molecule used in the production of the aqueous alkaline solution-soluble resin (A) of the present invention include hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether. Phenyl diglycidyl ether such as bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 Bisphenol type epoxy compounds such as 3-hexafluoropropane epoxy compound; hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis ( 4-hydroxyphenyl) Hydrogenated bisphenol type epoxy compounds such as epoxy compounds of 1,1,1,3,3,3-hexafluoropropane; halogenated bisphenol types such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins Epoxy compounds; Alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether; Aliphatic diglycidyl ethers such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether Compound; polysulfide type diglycidyl ether compound such as polysulfide diglycidyl ether; biphenol type epoxy resin and the like, preferably bisphenol-A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol -A type epoxy resin, hydrogenated bisphenol -F type epoxy resin is preferable.

The second reaction is a reaction in which an epoxy compound (c) having two epoxy groups in the molecule is added to the carboxyl group of the ester compound (x) obtained in the first reaction.
In the second reaction, the epoxy group of the epoxy compound (c) having two epoxy groups in the molecule is 0.1 to 3 equivalents, more preferably 1 equivalent of the carboxyl group generated in the first reaction. It is preferable to charge 0.2 to 1 equivalent. When this value is less than 0.1, the molecular weight becomes low and problems of photosensitivity and heat resistance are likely to occur. If this value exceeds 3, gelation tends to occur during the third reaction.
As reaction temperature, it is 60-180 degreeC, for example, Preferably it is 80-150 degreeC. The reaction time is 2 to 15 hours, preferably 3 to 10 hours.

  Examples of the polybasic acid anhydride (b ′) used in the third reaction for producing the aqueous alkali-soluble resin of the present invention include the same compounds as the polybasic acid anhydride (b), and preferred compounds are also the same. It is. The polybasic acid anhydride (b ′) in the third reaction may be the same as or different from the polybasic acid anhydride (b) in the first reaction.

The third reaction is a reaction in which a polybasic acid anhydride (b ′) is added to the alcoholic hydroxyl group in the molecule of the compound obtained in the second reaction.
The amount of the polybasic acid anhydride (b ′) charged is equal to or less than the equivalent of the hydroxyl group produced in the second reaction, and the solid content acid value of the alkaline aqueous solution-soluble resin (A) of the present invention is 30 to 150 mgKOH / It is preferable to charge a calculation amount in the range of g. When this solid content acid value is less than 30 mgKOH / g, the alkaline aqueous solution solubility of the photosensitive resin composition is remarkably lowered, and in the worst case, development processing cannot be performed, and as a result, patterning cannot be performed. On the other hand, when the solid content acid value exceeds 150 mgKOH / g, the aqueous alkali solution becomes too soluble, which causes problems such as poor adhesion and pattern flow.
In the present invention, the solid content acid value is the amount (mg) of potassium hydroxide required to neutralize the acidity of the carboxylic acid in 1 g of the resin, and the acid value neutralizes 1 g of the solution containing the resin. The amount (mg) of potassium hydroxide required for the measurement is measured by a normal neutralization titration method according to JIS K0070. If the concentration of the resin in the solution is known, the solid content acid value can be calculated from the acid value of the solution.
As reaction temperature of 3rd reaction, it is 60-150 degreeC, for example, Preferably it is 80-120 degreeC. The reaction time is 2 to 10 hours, preferably 3 to 8 hours.

  In the first reaction and / or the third reaction, a catalyst is used in order to increase the reactivity of the acid anhydride, particularly dibasic acid monoanhydride and / or tribasic acid monoanhydride with an alcoholic hydroxyl group. It may be used. Specific examples of the catalyst include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, trimethylphosphine, triphenylstibine, methyltriphenylstibine, octanoic acid Examples thereof include chromium, zirconium octoate, diphenyl sulfide, and dimethyl sulfide.

  In the first, second and third reactions, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount of the thermal polymerization inhibitor used is 0.05 to 10% by weight. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-ditert-butyl-p-cresol and the like.

  The first, second, and third reactions are solvent-free or have no alcoholic hydroxyl group, specifically, ketones such as acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl Cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glue Esters such as dialkyl oxalate, dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the reactivity described later What is necessary is just to perform in a single or mixed solution, such as a crosslinking agent (C).

  The method for producing the alkaline aqueous solution-soluble resin (A) of the present invention is not limited to the above method.

  The photosensitive resin composition of the present invention contains the above alkaline aqueous solution-soluble resin (A), a photopolymerization initiator (B), a reactive crosslinking agent (C), and a curing component (D) as an optional component.

  The content ratio of the alkaline aqueous solution-soluble resin (A) is usually 15 to 70% by weight, preferably 20 to 60% by weight when the solid content of the photosensitive resin composition is 100% by weight.

  Examples of the photopolymerization initiator (B) contained in the photosensitive resin composition of the present invention include all compounds used for ordinary photopolymerization and curing. Specific examples thereof include benzoin, benzoin methyl ether, and benzoin. Benzoins such as ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, Acetophenones such as diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone 2-chloro Anthraquinones such as nthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone and 2-isopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4- Benzophenones such as benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide And phosphine oxides. The addition ratio of these is usually 1 to 30% by weight, preferably 2 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  These can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester May be used in combination with a polymerization accelerator such as a benzoic acid derivative. When these polymerization accelerators are used, the amount added is 100% by weight or less based on the photopolymerization initiator (B).

  Examples of the reactive crosslinking agent (C) contained in the photosensitive resin composition of the present invention include (meth) acrylic acid derivatives. Specific examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, half ester which is a reaction product of hydroxyl group-containing (meth) acrylate and acid anhydride of polycarboxylic acid compound, Polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, hydroxybivari Di (meth) acrylate (e.g., Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include poly (meth) acrylate as a reaction product of ε-caprolactone, dipentaerythritol poly (meth) acrylate, and epoxy (meth) acrylate as a reaction product of a mono- or polyglycidyl compound and (meth) acrylic acid.

Examples of the hydroxyl group-containing (meth) acrylate in the half ester which is a reaction product of the hydroxyl group-containing (meth) acrylate and the polycarboxylic acid anhydride in the reactive crosslinking agent (C) include 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and the like.
Examples of the acid anhydride of the polycarboxylic acid compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.
Examples of the mono- or polyglycidyl compound in the epoxy (meth) acrylate that is a reaction product of the mono- or polyglycidyl compound and (meth) acrylic acid in the reactive crosslinking agent (C) include, for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane poly Examples thereof include ethoxypolyglycidyl ether.
The addition ratio of these reactive crosslinking agents (C) is usually 2 to 40% by weight, preferably 5 to 30% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  Examples of the curing component (D) as an optional component contained in the photosensitive resin composition of the present invention include an epoxy compound and an oxazine compound. The curing component (D) reacts with the carboxyl groups and hydroxyl groups remaining in the resin coating after photocuring by heating, and is expected to have a linear and / or ladder-like molecular weight increase effect, and further has improved heat resistance. It is particularly preferably used when trying to obtain a cured coating film having excellent chemical resistance.

  Specific examples of the epoxy compound as the curing component (D) include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, a bisphenol-A type epoxy resin, Examples thereof include bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, and heterocyclic epoxy resins.

Examples of phenol novolac type epoxy resins include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Company), Epicoat 154 (made by Japan Epoxy Resin Co., Ltd.), RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.
Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR- 6650 (made by Union Carbide), ESCN-195 (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned.
Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.) and Epicoat E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicort E1032H60 (Japan Epoxy) Resin Co., Ltd.).
Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (all manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.); UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.) Bisphenol-F type epoxy resin and the like.
Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H (both manufactured by Nippon Kayaku Co., Ltd.), and bixylenol type YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.). An epoxy resin, YL-6121 (made by Japan Epoxy Resin Co., Ltd.) etc. are mentioned.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000, NC-7300 (both manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like.
Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).
Examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S (all manufactured by Nissan Chemical Industries, Ltd.).

  Examples of the oxazine compound as the curing component (D) include Bm type benzoxazine, Pa type benzoxazine, and Ba type benzoxazine (all manufactured by Shikoku Kasei Kogyo Co., Ltd.).

  Among these, NC-3000 and YX-4000 which are biphenol type epoxy resins, and TEPIC-L, TEPIC-H and TEPIC-S which are heterocyclic epoxy resins are preferable as the curing component (D).

  When the curing component (D) is added, the addition ratio is the equivalent calculated from the solid content acid value of the alkaline aqueous solution-soluble resin (A) of the present invention and the amount used, that is, the alkaline aqueous solution-soluble resin (A). An amount of 200% or less of the equivalent of the epoxy group in the curing component (D) with respect to the carboxyl group contained in is preferable. When this amount exceeds 200%, the developability of the photosensitive resin composition of the present invention is remarkably lowered, which is not preferable.

  The photosensitive resin composition of the present invention further contains various fillers and additives as required, such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay. Fillers such as Aerosil; Thixotropic agents such as Aerosil; Colorants such as phthalocyanine blue, phthalocyanine green, and titanium oxide; Compositions such as silicone and fluorine leveling agents and defoamers; Polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether It can be added for the purpose of enhancing various properties of the product. Further, a thermosetting catalyst such as melamine may be added.

  In addition, although the said hardening component (D) may be mixed with the said resin composition previously, it can also be mixed and used before application | coating to a printed wiring board. That is, it is blended into a two-pack type consisting mainly of the alkaline aqueous solution-soluble resin (A) component, a main agent solution containing an epoxy curing accelerator and the like, and a curing agent solution mainly containing a curing component (D). In this case, these are mixed and used. As a solvent in the case of using as a solution, the solvent in the synthesis of the aqueous alkali solution-soluble resin (A) may be used as it is, or the solvent exemplified above as a solvent in the reaction may be used separately. You may mix and use.

  The photosensitive resin composition of the present invention can also be used as a dry film type solder mask having a structure in which the resin composition is sandwiched between a support film and a protective film.

  The photosensitive resin composition (liquid or film-like) of the present invention is useful as a resist material such as an insulating material between electronic components, an optical waveguide connecting optical components, a solder mask for printed circuit boards, and a coverlay. In addition, it can also be used as a color filter, printing ink, sealant, paint, coating agent, adhesive and the like.

  The present invention also includes a method for producing a cured product in which the photosensitive resin composition is cured by irradiation with active energy rays such as ultraviolet rays. Curing by irradiation of active energy rays such as ultraviolet rays can be carried out by a conventional method. For example, when ultraviolet rays are irradiated, ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, ultraviolet light emitting lasers (excimer lasers, etc.) are generated. An apparatus may be used.

The cured product of the photosensitive resin composition of the present invention is a substrate, for example, a resist film, an interlayer insulating material for a build-up method, or an optical waveguide as a printed circuit board, an optoelectronic circuit board or an electrical / electronic / optical component such as an optical circuit board. Used for. Specific examples of articles having these base materials include home appliances such as computers and liquid crystal displays, and mobile devices such as mobile phones.
The thickness of the cured product layer is about 0.5 to 160 μm, and preferably about 1 to 100 μm.

A solder mask for a flexible printed wiring board, an interlayer insulating film for a multilayer printed wiring board, or a photosensitive optical waveguide comprising the steps of applying, photocuring, alkali treatment and heat treatment of the photosensitive resin composition of the present invention This manufacturing method is also included in the present invention. For example, when specifically explaining a flexible printed wiring board, when using the liquid resin composition described above, a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, etc. The photosensitive resin composition of this invention is apply | coated by the method of 0.5-160 micrometers by the method of this, and it is normally dried at the temperature of 50-110 degreeC, Preferably it is 60-100 degreeC, and forms a coating film. Thereafter, an active energy ray such as ultraviolet rays is irradiated to the coating film directly or indirectly through a photomask in which an exposure pattern such as a negative film is formed, usually at an intensity of about 10 to 2000 mJ / cm ² , and the unexposed portion is described later. Using the liquid, development is performed, for example, by spraying, rocking dipping, brushing, scrubbing, or the like. Irradiation with ultraviolet rays as necessary, followed by heat treatment usually at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., is excellent in resistance to gold plating, and has high insulation, heat resistance, solvent resistance, and acid resistance. A printed wiring board having a permanent protective film satisfying various properties such as property, adhesion, and flexibility is obtained.

Examples of the alkaline aqueous solution used for the development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, and tetramethyl hydroxide. Examples include organic alkaline aqueous solutions such as ammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
The concentration of these aqueous alkaline solutions is about 0.1 to 5% by weight, preferably about 0.5 to 3% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example.

Example 1
KAYARAD R-115 (Nippon Kayaku Co., Ltd. bisphenol-A type epoxy acrylate, molecular weight 508.52) as a diol compound (a) having an ethylenically unsaturated group in the molecule in a 2 L 4-neck flask 508. 52 g (1.00 mol), 200.14 g (2.00 mol) of succinic anhydride as the polybasic acid anhydride (b), 303.71 g of diethylene glycol monoethyl ether acetate as the solvent, and 2,6 as the polymerization inhibitor -3.04 g of di-tert-butyl-p-cresol and 3.04 g of triphenylphosphine as a catalyst were charged and reacted at a temperature of 98 ° C for 4 hours. It was 158.36 mgKOH / g when the solid content acid value after reaction was measured. Next, RE310S (Nippon Kayaku Co., Ltd. bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184 g / equivalent) as an epoxy compound (c) having two epoxy groups in the molecule was added to this reaction solution. 0.08 g and 78.86 g of diethylene glycol monoethyl ether acetate as a solvent were added and reacted at a temperature of 98 ° C. for 10 hours. It was 62.86 mgKOH / g when the solid content acid value after reaction was measured. Next, 71.97 g (0.72 mol) of succinic anhydride as a polybasic acid anhydride (b ′) and 136.85 g of diethylene glycol monoethyl ether acetate as a solvent were added to this reaction solution, and reacted at 98 ° C. for 5 hours. A resin solution containing 65% by weight of the aqueous alkali solution-soluble resin (A) of the present invention was obtained. This resin solution is designated as A-1. When the acid value was measured, it was 65 mgKOH / g (solid content acid value: 100 mgKOH / g).

Example 2
540.18 g of R-9467 (Nippon Kayaku Co., Ltd. bisphenol-A type epoxy methacrylate, molecular weight 540.18) as a diol compound (a) having an ethylenically unsaturated group in the molecule in a 2 L four-necked flask (1.00 mol), 304.30 g (2.00 mol) of tetrahydrophthalic anhydride as the polybasic acid anhydride (b), 361.92 g of propylene glycol monomethyl ether acetate as the solvent, and 2,6 as the polymerization inhibitor -3.62 g of di-tert-butyl-p-cresol and 3.62 g of triphenylphosphine as a catalyst were charged and reacted at a temperature of 98 ° C for 5 hours. The solid content acid value after the reaction was measured and found to be 132.89 mgKOH / g. Next, in this reaction solution, 165 g of Epicoat 806 (Japan Epoxy Resin Co., Ltd. bifunctional bisphenol F type epoxy resin, epoxy equivalent 165 g / equivalent) as an epoxy compound (c) having two epoxy groups in the molecule, As a solvent, 70.71 g of propylene glycol monomethyl ether acetate was added and reacted at a temperature of 98 ° C. for 10 hours. It was 55.58 mgKOH / g when the solid content acid value after reaction was measured. Next, 97.32 g (0.97 mol) of succinic anhydride as an acid anhydride (b ′) and 163.34 g of propylene glycol monomethyl ether acetate as a solvent were added to this reaction solution and reacted at 98 ° C. for 5 hours. A resin solution containing 65% by weight of the aqueous alkali solution-soluble resin (A) of the invention was obtained. This resin solution is designated as A-2. When the acid value was measured, it was 65 mgKOH / g (solid content acid value: 100 mgKOH / g).

Example 3
(A-1) obtained in Example 1 was mixed at a blending ratio shown in Table 1 and kneaded with a three-roll mill to obtain a photosensitive resin composition of the present invention. This was applied to a printed circuit board by a screen printing method so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% by weight aqueous sodium carbonate solution to remove the resin in the non-irradiated part. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film. For coatings and cured products, as described below, tackiness, developability, resolution, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating Resistance, PCT resistance, and thermal shock resistance were tested, and the results are shown in Table 2.
Example 4
(A-2) obtained in Example 2 was mixed at a blending ratio shown in Table 1 and kneaded with a three-roll mill to obtain a photosensitive resin composition of the present invention. This was applied to a printed circuit board by a screen printing method so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% by weight aqueous sodium carbonate solution to remove the resin in the non-irradiated part. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film. For coatings and cured products, as described below, tackiness, developability, resolution, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating Resistance, PCT resistance, and thermal shock resistance were tested, and the results are shown in Table 2.
Comparative Example Using KAYARAD ZFR-1122 (alkali developable polyfunctional BisF epoxy acrylate; reaction product of hydroxyl group and tetrahydrophthalic anhydride formed by reaction of epoxidized bisphenol F with acrylic acid) manufactured by Nippon Kayaku Co., Ltd. The mixture was mixed at the blending ratio shown in Table 1 and kneaded with a three-roll mill to obtain a photosensitive resin composition. This was applied to a printed circuit board by a screen printing method so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% by weight aqueous sodium carbonate solution to remove the resin in the non-irradiated part. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film. For coatings and cured products, as described below, tackiness, developability, resolution, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating Resistance, PCT resistance, and thermal shock resistance were tested, and the results are shown in Table 2.

[Table 1] Composition content of photosensitive resin composition
Examples Comparative examples
Note 3 4
Resin solution A-1 46.55
A-2 46.55
Comparative resin solution ZFR-1122 46.55
Cross-linking agent (C)
DPCA-60 * 1 6.06 6.06
HX-220 * 2 6.06
Photopolymerization initiator (B)
Irgacure 907 * 3 4.54 4.54 4.54
DETX-S * 4 0.91 0.91 0.91
Curing component (D)
YX-4000 * 5 18.31 18.31 18.31
Thermosetting catalyst Melamine 1.00 1.00 1.00
Filler Barium sulfate 15.15 15.15 15.15
Phthalocyanine blue 0.61 0.61 0.61
Additive BYK-354 * 6 0.39 0.39 0.39
KS-66 * 7 0.69 0.69 0.69
Solvent CA * 8 4.54 4.54 4.54

* 1 Nippon Kayaku Co., Ltd .: ε-caprolactone-modified dipentaerythritol hexaacrylate * 2 Nippon Kayaku Co., Ltd .: ε-caprolactone-modified hydroxypivalate neopentyl glycol diacrylate * 3 Ciba Specialty Chemicals 2-Methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane * 4 Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone * 5 Japan Epoxy Resin Co., Ltd .: Bifunctional bixylenol Type Epoxy Resin * 6 Made by Big Chemie: Leveling Agent * 7 Made by Shin-Etsu Chemical Co., Ltd .: Antifoaming Agent * 8 Made by Osaka Organic Chemicals Co., Ltd .: Carbitol acetate

The test method and evaluation method are as follows.
(Tackiness) Absorbent cotton was rubbed on the dried film applied to the substrate, and the tackiness of the film was evaluated.
○ ·········· Do not stick absorbent cotton.
× ··· Absorbent cotton lint sticks to the membrane.

(Developability) Development is performed with a 1% by weight aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the time until the coating film is completely removed is measured.

(Resolution) A negative pattern of 20, 25, 30, 35, 40, 45, and 50 μm is brought into close contact with the dried coating film, and irradiated with ultraviolet rays having an integrated light quantity of 200 mJ / cm ² . Next, development is performed with a 1% by weight aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern is observed with a microscope to confirm the fineness of patterning without peeling or jagged lines. .

(Photosensitivity) Step tablet 21 (manufactured by Kodak Co., Ltd.) is brought into close contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 500 mJ / cm ² . Next, development is performed with a 1% by weight aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of stages of the coating film remaining without development is confirmed.

(Surface gloss) The dried coating film is exposed to 500 mJ / cm ² of ultraviolet rays. Next, development is performed with a 1% by weight aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the cured film after drying is measured with a gloss checker IG-320 (manufactured by Horiba, Ltd.).

(Substrate sled) The following criteria were used.
○ ········································································· •

(Flexibility) The cured film is bent at 180 ° C. and observed. The following criteria were used:
○ ···· No crack on the film surface × ··· The film surface breaks

(Adhesiveness) According to JIS K5400, 100 test pieces having 1 mm diameters were made on a test piece, and a peeling test was performed using cello tape (registered trademark). The peeled state of the goblet was observed and evaluated according to the following criteria.
○ ···································

(Pencil hardness) Evaluation was performed according to JIS K5400.

(Solvent resistance) The test piece is immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·······

(Acid resistance) The test piece is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·········

(Heat resistance) A rosin flux was applied to a test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with Cellotape (registered trademark) was conducted, and the following criteria were evaluated.
○ ··· There is no abnormality in the appearance of the coating film and there is no swelling or peeling × ········

(Gold plating resistance) The test substrate was immersed in an acidic degreasing solution at 30 ° C. (20 vol% aqueous solution of Metex L-5B, manufactured by Nippon McDermitt), washed with water, and then into a 14.4 wt% ammonium persulfate aqueous solution. After being immersed for 3 minutes at room temperature, it was washed with water, and further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution for 1 minute at room temperature and then washed with water. Next, this substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate Ni-865M). Was immersed in a 20 vol% aqueous solution, pH 4.6) for 20 minutes, nickel-plated, and then immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Next, the test substrate was immersed for 10 minutes in a gold plating solution at 95 ° C. (Meltex, aqueous solution of Aurolectroles UP 15 vol% and potassium gold cyanide 3 vol%, pH 6), electroless gold plating was performed, and then washed with water. It was immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. Cellotape (registered trademark) was adhered to the obtained electroless gold plating evaluation substrate, and the state when peeled off was observed and evaluated according to the following criteria.
○ ···· No abnormality at all ····· Slightly peeled

(PCT resistance) After leaving the test substrate in water at 121 ° C. and 2 atm for 96 hours, it was confirmed whether there was any abnormality in appearance and a peeling test using cello tape (registered trademark), and evaluated according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film, and there is no swelling or peeling × ·········

(Thermal shock resistance) The test piece was subjected to thermal history with -55 ° C / 30 minutes and 125 ° C / 30 minutes as one cycle, and after 1000 cycles, the test piece was observed with a microscope and evaluated according to the following criteria.
○ ······················································ /

[Table 2] Evaluation Results Example 3 4 Comparative Example Evaluation Item Tackiness ○ ○ ○
Developability 15 25 42
Resolution 30 30 30
Photosensitivity 10 13 8
Surface gloss 88 85 87
Substrate sled ○ ○ △
Flexibility ○ ○ ○
Adhesiveness ○ ○ ○
Pencil hardness 6H 6H 6H
Solvent resistance ○ ○ ○
Acid resistance ○ ○ ○
Heat resistance ○ ○ ○
Gold plating resistance ○ ○ ○
PCT resistance ○ ○ ○
Thermal shock resistance ○ ○ ○

Example 5
54.44 g of the resin solution (A-2) obtained in Example 2, 3.54 g of HX-220 (Nippon Kayaku Co., Ltd. bifunctional acrylate resin) as the reactive crosslinking agent (C), photopolymerization initiator (B) Irgacure 907 (Bantico photopolymerization initiator) 4.72 g and Kayacure DETX-S (Nippon Kayaku Co., Ltd. photopolymerization initiator) 0.47 g, Curing component (D) YX-8000 ( 14.83 g of bifunctional hydrogenated bisphenol-A type epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 202.06 g / equivalent), 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent are added. The mixture was kneaded with a bead mill and uniformly dispersed to obtain a photosensitive resin composition of the present invention.

  The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. A polyethylene film to be a protective film was attached to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm / polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

Next, ultraviolet rays were irradiated using an ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern (irradiation amount: 500 mJ / cm ² ). After the irradiation, the support film was peeled off from the resin and developed with a 0.25 wt% tetramethylammonium aqueous solution for 30 seconds to dissolve and remove unirradiated portions. After washing with water and drying, the printed circuit board was heated and reacted for 30 minutes with a hot air dryer at 150 ° C. to obtain a cured film. The obtained cured product had good transparency and a 50 μm pattern was resolved.

Example 6
19.8 g of the resin solution (A-1) obtained in Example 1, 13.4 g of DPHA (Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate) and PET-30 (Japan) as the reactive crosslinking agent (C) 4.0 g of pentaerythritol triacrylate manufactured by Kayaku Co., Ltd. 45.1 g of MEK-ST (organosilica sol MEK-ST manufactured by Nissan Chemical Co., Ltd.) as a modifier (additive for hard coat), photopolymerization started As the agent (B), 0.9 g of Irg-184 (manufactured by Ciba Specialty Chemicals 1-hydroxy-cyclohexyl-phenyl-ketone) and 0.2 g of lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by BASF Japan), 16.6 g of methyl ethyl ketone is blended as a solvent, and the sensitivity comprising the photosensitive resin of the present invention. To obtain a sexual coating composition.

  The obtained composition was applied to an untreated polyester film (HSL manufactured by Teijin Ltd., film thickness 75 μm) using a bar coater (No. 20), and left for 1 minute in a hot air dryer at 80 ° C. Using a 120 W / cm high-pressure mercury lamp in an air atmosphere, ultraviolet rays were irradiated at a distance of 10 cm at a conveyor speed of 5 m / min to obtain a film having a cured product layer.

  When the obtained cured product layer was subjected to adhesion, pencil hardness, and impact resistance tests by the above methods, good results were obtained in each test.

As is apparent from the above results, the alkaline aqueous solution-soluble resin of the present invention and the photosensitive resin composition using the same have no tackiness and high sensitivity, and the cured film also has solder heat resistance, chemical resistance, Excellent electrical properties such as gold plating resistance, high insulation, no cracks on the surface of the cured product, and even when using a thinned substrate, the substrate is not warped, printed circuit board, optical waveguide, photosensitive It is suitable for paint films.

Claims (8)

A polybasic acid anhydride (b) is reacted with a diol compound (a) having an ethylenically unsaturated group in the molecule, or a diol compound (d) other than the diol compound (a) and the compound (a). The carboxyl group of the resulting ester compound (x) is reacted with an epoxy compound (c) having two epoxy groups in the molecule, and the resulting diol and polybasic acid anhydride (b ′) are reacted. Obtained aqueous alkali-soluble resin (A). The diol compound (a) is a reaction product of an epoxy compound having two epoxy groups in the molecule and (meth) acrylic acid or cinnamic acid, and the polybasic acid anhydride is dibasic acid monoanhydride and / or The alkaline aqueous solution-soluble resin (A) according to claim 1, which is a tribasic acid monoanhydride. The alkaline aqueous solution-soluble resin (A) according to claim 1 or 2, wherein the solid content acid value of the alkaline aqueous solution-soluble resin (A) is 30 to 150 mgKOH / g. 1. The aqueous alkali solution-soluble resin (A) according to any one of claims 1 to 3,
2. Photopolymerization initiator (B),
3. Reactive crosslinking agent (C),
4). Curing component (D) as an optional component
Containing a photosensitive resin composition. A method for producing a cured product, wherein the photosensitive resin composition according to claim 4 is irradiated with active energy rays. The base material which has a layer of the hardened | cured material by the manufacturing method of Claim 5. An article comprising the substrate according to claim 6. A solder mask for a printed wiring board, a solder mask for a flexible printed wiring board, and a multilayer printed wiring comprising the steps of applying the photosensitive resin composition according to claim 4, photocuring, alkali treatment and heat treatment. A method for producing an interlayer insulating film for a plate, a photosensitive optical waveguide, or a photosensitive coating film.