JP2002014466A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of ensuring enhanced photosensitivity and resolution and giving a cured coating excellent in resistance to electroless gold plating. SOLUTION: The photosensitive resin composition contains (A-1) a modified copolymer obtained by adding the epoxy group of an alicyclic epoxy group- containing unsaturated compound to part of the acid groups of a copolymer comprising (a) β-carboxyethyl acrylate, (b) an acid group-containing unsaturated compound and (c) a (meth)acrylic ester and (B) at least one monomer selected from the group comprising acetoacetoxyethyl acrylate, acryloylmorpholine and tetrahydrofurfuryl acrylate or contains a modified copolymer obtained by adding the epoxy group of an alicyclic epoxy group-containing unsaturated compound to part of the acid groups of a copolymer comprising the monomers (a), (b), (c) and (B) and further contains (C) a resin having two or more unsaturated groups in one molecule and a cyclic skeleton and curable with active energy beams, (D) a diluent and (E) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, and more particularly to a printed wiring board material such as a solder resist, a plastic relief material, a member for a flat panel display (FPD), a coating protective film, a glass protective film, The present invention relates to a novel photosensitive resin composition suitably used for stone etching, metal precision processing, and the like.

[0002]

2. Description of the Related Art Solder resist is a resist for protecting a circuit from solder when electronic components are mounted on the surface of a printed wiring board, and the entire surface of a circuit conductor excluding mounting pads (solder pads). Coated. As described above, the solder resist functions as a protective film for preventing the circuit conductor from being directly exposed to the air and being oxidized or corroded by moisture, and also flows out or adheres to an unnecessary portion of the solder. It also functions as a solder dam that prevents Therefore, the solder resist is required to have various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, alkali resistance, acid resistance, and plating resistance.

[0003] As one of the conventional techniques for forming a solder resist requiring such various properties, a thermosetting or ultraviolet curable composition is printed on a substrate by a screen printing method, and the coating film is applied. Examples of the method include curing by ultraviolet light or heat (JP-B-51-14044, JP-B-61-14044).
No. 48800). However, due to the recent miniaturization and high functionality of electronic devices, the demand for improvement in circuit pattern density and pattern accuracy has been increasing even in wiring boards, and conventional thermosetting or ultraviolet-curing compositions have been used. With the screen printing method used, satisfactory results have not been obtained due to limitations in printing accuracy. Moreover, in the screen printing method, phenomena such as bleeding, bleeding, and sagging at the time of printing occur, and troubles such as solder not attaching to the solder pad at a predetermined position were observed.

On the other hand, another conventional technique which can solve the above problem and improve the pattern accuracy is to use a photosensitive resin composition of a solvent development type or an alkali development type to expose,
A photo method for forming a pattern by development is known. Particularly, recently, due to the problem of environmental pollution, as a photosensitive resin composition used in such a photo method, there is a tendency to use a composition of a solvent development type to an alkali development type. As such an alkali-developing type photosensitive resin composition, for example, a photosensitive prepolymer obtained by adding a polybasic anhydride to a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid as a base polymer (See JP-A-61-243869, JP-A-7-50473, and JP-B-7-17737).

On the other hand, a resin composition containing a polymer obtained by adding an alicyclic epoxy group-containing unsaturated compound to a poly (meth) acrylic resin has been proposed. However, the composition according to this proposal has a problem that the photosensitivity is not yet sufficient and the gold plating resistance is poor such as peeling of the coating film under severe conditions such as gold plating.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems of the prior art, and its main purpose is to satisfy various characteristics required for a solder resist, An object of the present invention is to provide a photosensitive resin composition capable of dramatically improving photosensitivity and resolution and obtaining a cured film having excellent electroless gold plating resistance.

[0007]

According to a first aspect of the present invention, there is provided (A-1) (a) β
-Carboxyethyl acrylate (hereinafter, “β-CE
A ". ), (B) adding an epoxy group of an alicyclic epoxy group-containing unsaturated compound to some acid groups of a copolymer comprising an acid group-containing unsaturated compound and (c) a (meth) acrylic ester; The resulting modified copolymer, (B) at least one monomer selected from the group consisting of acetoacetoxyethyl acrylate, acryloylmorpholine and tetrahydrofurfuryl acrylate, (C)
Photosensitivity characterized by containing an active energy ray-curable resin having two or more unsaturated groups in one molecule and having a cyclic skeleton, (D) a diluent, and (E) a photopolymerization initiator. A resin composition is provided.

According to a second aspect of the present invention, (A
-2) a group consisting of (a) β-CEA, (b) an acid group-containing unsaturated compound, (c) (meth) acrylate, and (d) acetoacetoxyethyl acrylate, acryloylmorpholine and tetrahydrofurfuryl acrylate. (C) a modified copolymer obtained by adding an epoxy group of an alicyclic epoxy group-containing unsaturated compound to a part of acid groups of a copolymer composed of at least one monomer selected from the group consisting of: Resin composition comprising an active energy ray-curable resin having two or more unsaturated groups and having a cyclic skeleton, (D) a diluent, and (E) a photopolymerization initiator. Is provided.

In a particularly preferred embodiment, the active energy ray-curable resin (C) is an esterified product of an epoxy group formed by an esterification reaction between (e) a novolak type epoxy compound and (f) an unsaturated monocarboxylic acid. A photosensitive prepolymer (C-1), and (g) a diisocyanate and (h) a (meth) having one hydroxyl group in one molecule.
At least one selected from the group consisting of a photosensitive prepolymer (C-2) obtained by reacting a reaction product with an acrylate with a secondary hydroxyl group of the photosensitive prepolymer (C-1); The mixing ratio of the component (A) and the component (C) is in the range of 100: 2 to 100: 50 (by mass).

In still another embodiment, the photosensitive resin composition of the present invention comprises (F) an epoxy compound and / or (G)
It is characterized by containing a latent cured adhesion-imparting agent and / or (H) an inorganic filler. The alicyclic epoxy group-containing unsaturated compound is preferably 3,4-cyclohexylmethyl (meth) acrylate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises β-CEA (a), an acid group-containing unsaturated compound (b), and a (meth) acrylate (c) which constitute the composition. To a modified copolymer (A) obtained by adding an epoxy group of an alicyclic epoxy group-containing unsaturated compound to a part of acid groups of the copolymer, acetoacetoxyethyl acrylate,
The first feature is that at least one monomer selected from the group consisting of acryloylmorpholine and tetrahydrofurfuryl acrylate is added as a composition component or is previously introduced into the skeleton of the copolymer. . In addition, the photosensitive resin composition of the present invention contains 2 per molecule.
The second feature is that the active energy ray-curable resin (C) having at least one unsaturated group and having a cyclic skeleton is blended. This provides a photosensitive resin composition that satisfies various characteristics required for a solder resist, can dramatically improve photosensitivity and resolution, and can provide a cured film having excellent electroless gold plating resistance. can do.

In the photosensitive resin composition of the present invention, the β-CEA (a) has the following structural formula, and the unsaturated double bond forming the main skeleton of the copolymer resin has a carboxyl group. And the unsaturated double bond of the alicyclic epoxy group-containing unsaturated compound that undergoes an addition reaction with the carboxyl group is a position not affected by steric hindrance by the main chain. As a result, the photosensitive resin composition of the present invention has improved photosensitivity.

Embedded image

The acid group-containing unsaturated compound (b) may be any compound having an unsaturated group in the molecule and at least one acid group, and is not limited to a specific compound. Specific examples thereof include (meth) acrylic acid, vinylphenols, and maleic acid having two or more carboxyl groups in a molecule, and these can be used alone or in combination of two or more. In the present invention, (meth) acrylic acid is preferable among these. In this specification, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and the same applies to other similar expressions.

Specific examples of the (meth) acrylate (c) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate alkyl esters such as (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (Meth) acrylates having a hydroxyl group such as caprocactone-modified 2-hydroxyethyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, and hydroxynorbornyl (meth) acrylate; Toxiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylate and the like.

The molar ratio of the components (a), (b) and (c) constituting the copolymer component (A-1) in the present invention can be arbitrarily selected. )
/ (B) / (c) is 2 to 50/20 to 60/30 to 80
And more preferably 5 to 4
The range is 0/30 to 60/30 to 50. The reason for this is that if the molar ratio of β-CEA (a) is smaller than the above range, the photosensitivity is significantly reduced, while if it exceeds the above range, the dryness of the dry coating film to the touch is reduced.

In the copolymer component (A-2) according to another embodiment of the present invention, the copolymer component (A), (b), (c)
The amount of at least one monomer (d) selected from the group consisting of acetoacetoxyethyl acrylate, acryloylmorpholine and tetrahydrofurfuryl acrylate to be introduced into the resin skeleton of the copolymer consisting of But preferably (a),
The amount is 1 to 20 parts by mass based on 100 parts by mass of the copolymer resin composed of (b) and (c). When the component (d) is added to the composition as the additional component (B), it is desirable to further increase the amount of the component (A) to be used.
It is added in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the copolymer resin composed of (b) and (c). These reasons are:
When the introduction amount or the addition amount of the monomer component (d) or the additional component (B) is less than the above range, the obtained cured film has insufficient resistance to electroless gold plating. This is because further improvement in plating resistance cannot be expected, and the dryness of the dry coating film to the touch is adversely affected.

In the present invention, the aforementioned (a), (b),
(C) a copolymer, or (a), (b),
The epoxy resin of the alicyclic epoxy group-containing unsaturated compound is added to a part of the acid groups of the copolymer composed of (c) and (d) in the presence of a catalyst to provide a photosensitive resin composition of the present invention. Modified copolymer (A-1) or (A-2) serving as a photosensitive component
Is obtained. The unsaturated compound having an alicyclic epoxy group may be a compound having one radically polymerizable unsaturated group and an alicyclic epoxy group in one molecule, and is not limited to a specific compound. Specific examples thereof include compounds represented by the following general formulas (1) to (13).

Embedded image In each formula, R ¹ is a hydrogen atom or a methyl group, and R ² has 1 to 1 carbon atoms.
An alkylene group of 10, R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, and k represents 0 or an integer of 1 to 10. These alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more. Among these,
3,4-Epoxycyclohexylmethyl (meth) acrylate is preferred.

It is desirable that the alicyclic epoxy group-containing unsaturated compound be added in an amount of 5 to 50 mol% based on the modified copolymer. The reason for this is that if the added amount is less than 5 mol%, the resulting photosensitive resin composition will have poor ultraviolet curability, and the physical properties of the cured film will be reduced. On the other hand, if the added amount exceeds 50 mol%, the storage stability of the resin will be poor.

The modified copolymer (A) thus obtained
-1) or (A-2) has an acid value of 10 to 150 mg.
It is preferable to adjust to a range of KOH / g. The reason for this is that if the acid value is less than 10 mgKOH / g, it is difficult to remove the unexposed portions with a weak alkaline aqueous solution, while if the acid value exceeds 150 mgKOH / g, the water resistance and electrical properties of the cured film become poor. This is because problems such as inferiority occur. Also,
The modified copolymer (A-1) or (A-2) preferably adjusts the weight average molecular weight to a range of 5,000 to 100,000. The reason is that the weight average molecular weight is 5,000.
If it is less than 0, the dryness of the dry coating film is extremely poor,
On the other hand, if the weight average molecular weight exceeds 100,000, there arises a problem that the developability of the photocurable film and the storage stability of the composition are significantly deteriorated.

The catalyst used for adding the alicyclic epoxy group-containing unsaturated compound to some of the acid groups of the copolymer (acid group-containing resin) is dimethylbenzylamine, triethylamine, tetramethylamine or the like. Tertiary amines such as ethylenediamine and tri-n-octylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and tetrabutylammonium bromide; alkyl ureas such as tetramethyl urea; alkyl guars such as tetramethyl guanidine Examples include metal compounds represented by dinin, cobalt naphthenate, etc., organometallic complexes, phosphines such as triphenylphosphine, and salts thereof, and tertiary phosphines represented by triphenylphosphine are particularly preferred. Used That. These catalysts can be used alone or in combination of two or more, and the amount of the alicyclic epoxy group-containing unsaturated compound to be used is 0.01 to 10%.
%, Preferably 0.5 to 3.0% by mass. The reason is that if the amount of the catalyst is less than 0.01% by mass, the catalytic effect is low, while if it exceeds 10% by mass, the catalytic effect cannot be expected to increase and it is not necessary to add more amount. .

Next, the active energy ray-curable resin (C) constituting the photosensitive resin composition of the present invention is a photosensitive resin having two or more unsaturated groups in one molecule and having a cyclic skeleton. A prepolymer is used. Specifically, a photosensitive prepolymer (C-1) which is an esterified product of an epoxy group generated by an esterification reaction between (e) a novolak type epoxy compound and (f) an unsaturated monocarboxylic acid is used. And / or (g) a reaction product of a diisocyanate and (h) a (meth) acrylate having one hydroxyl group in one molecule with a secondary hydroxyl group of the photosensitive prepolymer (C-1). The photosensitive prepolymer (C-2) obtained by the reaction is suitably used.

Examples of the novolak type epoxy compound (e) include YDCN-701 and YDCN manufactured by Toto Kasei Co., Ltd.
N-704; N-66 manufactured by Dainippon Ink and Chemicals, Inc.
5, N-680, N-695; EO manufactured by Nippon Kayaku Co., Ltd.
CN-102, EOCN-104; ECN-265, ECN-293, ECN-285, manufactured by Asahi Kasei Corporation
Cresol novolak type epoxy resin such as ECN-299, YDPN-638, YDP manufactured by Toto Kasei Co., Ltd.
N-602; DEN-4 manufactured by Dow Chemical Japan Co., Ltd.
31, DEN-438, DEN-439; EPN-1138, E manufactured by Ciba Specialty Chemicals Co., Ltd.
PN-1235, EPN-1299; phenol novolak type epoxy resins such as N-730 and N-770 manufactured by Dainippon Ink and Chemicals, Inc .; Further, a part of the novolak type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
It can be replaced with epoxy compounds such as bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, alicyclic epoxy resin, etc. It is particularly preferable to use a phenol novolak type epoxy compound as a solder resist for a wiring board.

Examples of the unsaturated monocarboxylic acid (f) include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid and the like. Half-esters of unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, or half-esters of saturated or unsaturated dibasic acids and unsaturated monoglycidyl compounds, for example Saturated or unsaturated dibasic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, itaconic acid, chlorendic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid and methyltetrahydrophthalic acid Anhydride and hydroxyethyl acrylate, hydroxypropyl acrylate, Roxybutyl acrylate, polyethylene glycol monoacrylate, glycerin acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and triglycidyl isocyanurate diacrylate or methacrylates corresponding to the above acrylates, or the saturated or unsaturated acrylates. A half ester obtained by reacting a saturated dibasic acid and glycidyl (meth) acrylate in an equimolar ratio by an ordinary method is used alone or in combination of two or more. Among them, from the viewpoint of photoreactivity. Acrylic acid is preferred.

The diisocyanates (g) include:
Tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluidine diisocyanate, lysine diisocyanate and the like are used.

The above (meth) acrylates having one hydroxyl group in one molecule (h) include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, glycerin diacrylate, and trimethylolpropanediene. Diacrylates such as acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and tris (hydroxyethyl) isocyanate, and methacrylates corresponding to these acrylates are used, and hydroxyethyl acrylate or pentaerythritol triacrylate is particularly preferable.

The compounding ratio of the components (A) and (C) used in the present invention is 100: 2 to 100: 50.
(Based on mass). When the compounding ratio of the component (C) is less than the above range, the rigidity of the component (A) cannot be sufficiently reduced, and the electroless gold plating resistance is not sufficient. On the other hand, when the blending ratio of the component (C) exceeds the above range, the dryness of the coating film after drying becomes poor, which is not preferable.

Next, as the diluent (D) constituting the photosensitive resin composition of the present invention, a photopolymerizable monomer and / or an organic solvent can be used. Representative photopolymerizable monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; and mono- or di-glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Acrylates; N, N-dimethylacrylamide;
Acrylamides such as N-methylol acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate; Polyhydric acrylates of these ethylene oxide or propylene oxide adducts; phenoxy acrylates, bisphenol A diacrylates and acrylates of these phenols such as ethylene oxide or propylene oxide adducts; glycerin diglycidyl ether;
Acrylates of glycidyl ether such as trimethylolpropane triglycidyl ether; melamine acrylate; and / or methacrylates corresponding to the above acrylates.

On the other hand, organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene Glycol ethers such as glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether; ethyl acetate;
Esters such as butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; Examples include petroleum solvents such as ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

The above-mentioned diluents (D) can be used alone or in combination of two or more. The preferred amount of the diluents is (A-1) or (A-2). )
It is preferable that the amount be 20 to 300 parts by mass with respect to 100 parts by mass. The purpose of use of this diluent is, in the case of a photopolymerizable monomer, to dilute the modified copolymer to make it easy to apply, and to enhance photopolymerizability,
On the other hand, in the case of an organic solvent, the modified copolymer is dissolved and diluted, whereby the modified copolymer is applied as a liquid, and then dried to form a film. Therefore, depending on the diluent to be used, either a contact type or a non-contact type in which a photomask is brought into contact with a coating film is used.

The photopolymerization initiator (E) constituting the photosensitive resin composition of the present invention includes, for example, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n Benzoins such as -butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxy-2-phenylacetophenone, 1,1-
Dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio)
Phenyl] -2-morpholino-1-propanone, N,
Acetophenones such as N-dimethylaminoacetophenone; 2,4-dimethylthiosanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4
Thioxanthones such as diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t
anthraquinones such as tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate;
Benzoic acid esters such as (dimethylamino) ethyl benzoate and p-dimethylbenzoic acid ethyl ester; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. .

These photopolymerization initiators (E) can be used alone or in combination of two or more. The amount of the photopolymerization initiators used is the same as that of the modified copolymer (A-1) or (A-2).
The range of 0.05 to 30 parts by mass relative to 0 parts by mass is preferred. In the present invention, for the purpose of accelerating the photopolymerization reaction by the photopolymerization initiator, a photopromoting agent can be further used in combination, and typical photopromoting agents include, for example, triethylamine, triethanolamine, Tertiary amines such as 2-dimethylaminoethanol; alkylphosphines represented by triphenylphosphine; β
And known photosensitizers such as thiols represented by thioglycol.

Next, as the epoxy compound (F) added as an optional component in the photosensitive resin composition of the present invention, an epoxy compound containing a known solid or liquid epoxy resin can be used. Specifically, Nippon Kayaku Co., Ltd. BPS-200, AC R Co., Ltd.
Bisphenol S-type epoxy resin such as EPX-30 manufactured by Dainippon Ink and Chemicals, Inc., Epicron EXA-1514; diglycidyl phthalate resin such as Blenmer DGT manufactured by NOF Corporation; T manufactured by Nissan Chemical Industries, Ltd.
Heterocyclic epoxy resin such as EPIC, Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd .; YX-400 manufactured by Yuka Shell Epoxy Co., Ltd.
Nippon Kayaku Co., Ltd. Nippon Kayaku Co., Ltd. Nippon Kayaku Co., Ltd. Nippon Kayaku Co., Ltd. Nippon Kayaku Co., Ltd. Co., Ltd. EPPN-201, EOCN-103, EO
CN-1020, EOCN-1025, ECN-278, ECN-292, ECN-, manufactured by Asahi Kasei Corporation
299, manufactured by Ciba Specialty Chemicals Co., Ltd.
ECN-1273, ECN-1299, Toto Kasei Co., Ltd.
YDCN-220L, YDCN-220HH, YD
CN-702, YDCN-704, YDPN-601,
YDPN-602, manufactured by Dainippon Ink and Chemicals, Inc. Epicron N-665, N-680, N-695, N-7
Novolak epoxy resins such as No. 70 and N-775: EPX8001, EPX-800 manufactured by Asahi Kasei Corporation
2, novolak type epoxy resin of bisphenol A such as EPPX-8060, EPPX-8061, Epicron N-880 manufactured by Dainippon Ink and Chemicals, Inc .; EPX-49-69, EPX-49- manufactured by Asahi Denka Kogyo KK 3
Chelate type epoxy resin such as 0; Y manufactured by Toto Kasei Co., Ltd.
Glyoxal type epoxy resin such as DG-414; YH-1402, ST-110 manufactured by Toto Kasei Co., Ltd., YL-931, YL-933 manufactured by Yuka Shell Epoxy Co., Ltd.
Amino group-containing epoxy resins such as; Epoxy TSR-601 manufactured by Dainippon Ink and Chemicals, EPX-84-2, EPX-4061 manufactured by Asahi Denka Kogyo Co., Ltd .; rubber-modified epoxy resins; Sanyo Kokusaku Pulp Co., Ltd. ) Made DC
Dicyclopentadiene phenolic epoxy resin such as E-400; silicone-modified epoxy resin such as X-1359 manufactured by Asahi Denka Kogyo Co., Ltd .; ε such as Plaxel G-402 and G-710 manufactured by Daicel Chemical Industries, Ltd.
Caprolactone-modified epoxy resin and the like can be used. In the present invention, it is possible to use a partially esterified product of these epoxy compounds with (meth) acrylic acid, and a compound or resin having an unsaturated group and an acid group obtained by adding an acid anhydride to the partially esterified product. .

The mixing ratio of the epoxy compound (F) is such that the modified copolymer (A-1) or (A-2) has a mass ratio of (A-1) or (A-2) to the modified copolymer (A-1) or (A-2): (E) = 5
The ratio is preferably set to 0:50 to 99: 1. The reason for this is that if the compounding ratio of the epoxy compound (E) exceeds the above range, in the case of the alkali developing type, the solubility of the unexposed portion in the developing solution is reduced, and the undeveloped portion is easily generated. This is because, in the case of the solvent development type, the film is easily eroded by the developer, and the coating film is liable to fall off or blister, which makes practical use difficult.

The carboxyl group of the modified copolymer (A-1) or (A-2) and the epoxy group of the epoxy compound (F) react by ring-opening polymerization. When an epoxy resin which is easily soluble in the agent (F) or another substance in the composition is used, the crosslinking is likely to proceed due to heat during drying. Therefore, when it is desired to suppress the above and increase the drying time, it is preferable to use the hardly soluble fine-grained epoxy resin alone or together with the easily soluble epoxy resin. However, since a hardly soluble epoxy resin has low reactivity, it is desirable to use a curing accelerator together.

As the latent curing adhesion promoter (G) added as an optional component, melamine, ethyldiamino-S-
Triazine, 2,4-diamino-S-triazine, 2,
4-diamino-6-tolyl-S-triazine, 2,4-
S-triazine compounds such as diamino-6-xylyl-S-triazine and derivatives thereof; guanamine, acetoguanamine, benzoguanamine, 3,9-bis [2-
(3,5-diamino-2,4,6-triazaphenyl)
Guanamines such as ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane; 2MZ, 2E4MZ, C11Z, C17 manufactured by Shikoku Chemicals Corporation
Z, 2PZ, 1B2HZ, 2MZ-CN, 2E4MZ-
CN, C11Z-CN, 2PZ-CN, 2P11Z-C
N, 2MZ-CNS, 2E4MZ-CNS, 2PZ-C
NS, 2MZ-AZINE, 2E4MZ-AZINE,
C11Z-AZINE, 2MA-OK, 2P4MHZ,
Imidazole such as 2PHZ and 2P4BHZ and derivatives thereof; diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, cyclohexylamine, m-xylylenediamine, 4,4'-diamino-3,3'diethyldiphenylmethane, diethylenetriamine, tetraethylenepentane Min, N-aminoethylpiverazine, isophoronediamine, dicyandiamide,
Urea, urea derivatives, polyamines such as polybasic hydrazide, their organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; trimethylamine, triethanolamine, N, N-dimethyloctylamine;
N, N-dimethylaniline, N-benzyldimethylamine, pyridine, N-methylpyridine, N-methylmorpholine, hexamethoxymethylmelamine, 2,4,6-tris (dimethylaminophenol), N-cyclohexyldimethylamine, Tertiary amines such as methylguanidine and m-aminophenol; organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexa Phosphonium salts such as decyltributylphosphonium chloride; quaternary ammonia such as benzyltrimethylammonium chloride, phenyltributylammonium chloride and benzyltrimethylammonium bromide Umushio; diphenyliodonium tetrafluoroboronate benzoate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenyl-thio pyrylium hexafluorophosphate, Ciba
Irgacure 2 manufactured by Specialty Chemicals Co., Ltd.
Photocationic polymerization catalysts such as 61; styrene-maleic acid resins, silane coupling agents, etc .; and S-triazine compounds are preferably used from the viewpoint of improving adhesiveness, adhesion and plating resistance. Such a latent curing adhesion imparting agent (G) can be used alone or in combination of two or more, and the amount of the latent curing adhesion imparting agent is 100% of the modified copolymer (A-1) or (A-2). 0.0 to parts by mass
The content is preferably 5 to 15 parts by mass.

The photosensitive resin composition of the present invention may optionally contain an inorganic filler (H) for the purpose of improving properties such as adhesion and hardness. Examples of the inorganic filler (H) include known inorganic powders such as barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. Can be blended. The compounding ratio is preferably 0 to 60% by mass of the photosensitive resin composition, and more preferably 5 to 40% by mass.

If necessary, known coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, hydroquinone, hydroquinone monomethyl ether, tert- Known thermal polymerization inhibitors such as butyl catechol, pyrogallol, and phenothiazine; known thickeners such as orben, bentone, and montmorillonite; silicone oils, fluorine oils, mineral oils such as liquid paraffin, and defoaming acrylic copolymers and the like Known additives such as agents, leveling agents and antioxidants can be blended.

Furthermore, diallyl phthalate prepolymer or diallyl isophthalate prepolymer, which is an allyl compound, can be added as an organic filler, and the addition thereof can improve chemical resistance. The amount of the organic filler to be added is preferably 30 parts by mass or less, more preferably 20 parts by mass or less based on 100 parts by mass of the modified copolymer (A-1) or (A-2). As the above prepolymer, Daiso Co., Ltd.
Daiso Dap, Daiso Isodap, and the like, and those having an average molecular weight of 2,000 to 30,000 are preferably used. Among them, the average molecular weight is 5,000 to 20,000
A diallyl isophthalate prepolymer of 0 is preferred.

Further, for the purpose of enhancing the impact resistance of the cured film, copolymers of ethylenically unsaturated compounds such as acrylates or polyhydric alcohols and saturated or unsaturated polybasic acid compounds are used. Known binder resins such as synthesized polyester resins, and polyester (meth) acrylates synthesized from polyhydric alcohols, saturated or unsaturated polybasic acid compounds and glycidyl (meth) acrylate, and polyhydric alcohols Known photosensitive oligomers such as urethane (meth) acrylates synthesized from diisocyanates and hydroxyl group-containing (meth) acrylates can be blended within a range that does not affect various properties as a solder resist mask.

However, among the above components, as for binder materials such as copolymers of ethylenically unsaturated compounds such as acrylates and polyester resins, copolymers containing no photosensitive group and known binder resins If a large amount is used, problems such as poor developability and sensitivity may occur. Therefore, the amount used is 10% by mass or less of the modified copolymer (A-1) or (A-2) (5% by mass of the entire composition). % Or less).

When a solder resist is formed by using the photosensitive resin composition of the present invention as described above, for example, the photosensitive resin composition is applied on a printed wiring board, preliminarily dried, and then subjected to a photomask. The resist pattern is formed by selectively exposing with an active energy ray and photopolymerizing, developing the unexposed portion with a developing solution to form a resist pattern, and then heating and thermosetting. Here, as a method of applying the photosensitive resin composition of the present invention on a substrate to form a coating film, known methods can be adopted, for example, screen printing, curtain coating, roll coating, spraying An appropriate coating method such as painting can be adopted.

The developer varies depending on the selection of the active energy ray-curable resin (modified copolymer A-1 or A-2), but includes cyclohexanone, xylene, tetramethylbenzene, butyl cellosolve, butyl carbitol, propylene glycol monomethyl. Organic solvents such as ether, cellosolve acetate, propanol, and propylene glycol; alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines; and surfactants An aqueous solution or the like can be used.

In particular, the photosensitive resin composition of the present invention is advantageous in that it can be developed with a dilute aqueous alkaline solution. That is, a specific prescription is to first apply the photosensitive resin composition of the present invention to a substrate at a desired thickness, and then apply
The organic solvent is volatilized by heating at ８０80 ° C. for 15 to 60 minutes, and then a mask on which a desired pattern with a transparent image portion is drawn is placed on the coating film of the substrate, and irradiated with active energy rays, preferably ultraviolet rays. To selectively expose a desired pattern. This causes the composition in the exposed areas of the coating to crosslink and become insoluble. Next, the unexposed area is developed and removed with a dilute alkaline aqueous solution. Desirably, the pattern thus obtained is irradiated with ultraviolet light,
Secondary curing is performed by applying heat at 0 to 200 ° C. or far infrared rays.
As the diluted alkaline aqueous solution used here, a known alkaline aqueous solution can be used, and a 0.5 to 5% by weight aqueous solution of sodium carbonate is generally used.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Note that “parts” and “%” are all based on mass unless otherwise specified.

Synthesis Example 1 325 g of dipropylene glycol monomethyl ether (MFDG, manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. After raising the temperature to 110 ° C., 37.6 g of β-CEA (β carboxyethyl acrylate), 201.9 g of methacrylic acid, 186.4 g of methyl methacrylate, MFDG 222
g and 12.0 g of t-butylperoxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O) were added dropwise over 3 hours. After dropping, a trunk polymer having a carboxyl group was synthesized by aging for 3 hours. Next, 289.2 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Cyclomer A200), 2.9 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added to the solution of the trunk polymer. At 100 ° C. for 10 hours. This reaction is
The reaction was carried out in a mixed atmosphere of air / nitrogen, whereby the acid value was 100 mgKOH / g, the double bond equivalent (resin weight per mole of unsaturated group) was 450, and the weight average molecular weight was 15,
000 (A-1) was obtained.

Synthesis Example 2 250 g of dipropylene glycol monomethyl ether (MFDG, manufactured by Nippon Emulsifier Co., Ltd.) was introduced into a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. After heating to 110 ° C., β-CEA (β-carboxyethyl acrylate) 26.3 g, methacrylic acid 141.2 g, methyl methacrylate 34.8 g, acetoacetoxyethyl methacrylate 26.3 g, MFDG 223 g,
And 12.0 g of t-butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O) was added dropwise over 3 hours. After dropping, a trunk polymer having a carboxyl group was synthesized by aging for 3 hours. Next, 202.2 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Cyclomer A200), 2.0 g of triphenylphosphine, and 1.0 g of methylhydroquinone were added to the solution of the trunk polymer. At 100 ° C. for 10 hours. This reaction is carried out in a mixed atmosphere of air / nitrogen, whereby an acid value of 10
A photocurable resin solution (A-2) having 0 mgKOH / g, a double bond equivalent of 450, and a weight average molecular weight of 15,000 was obtained.

Synthesis Example 3 250 g of propylene glycol monomethyl ether (manufactured by Daicel Chemical Industries, Ltd., MMPG) was introduced into a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. After heating to 110 ° C., 26.3 g of β-CEA (β-carboxyethyl acrylate), 141.2 g of methacrylic acid, 59.8 g of methyl methacrylate, 70.5 g of acryloylmorpholine, 223 g of MFDG, and t-butyl 12.0 g of peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O) was added dropwise over 3 hours. After this dropping, a trunk polymer having a carboxyl group was synthesized by aging for 3 hours. Next, 202.2 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Cyclomer A200) was added to a solution of the trunk polymer, and triphenylphosphine was used.
2.0 g, 1.0 g of methylhydroquinone and 1
The reaction was performed at 00 ° C. for 10 hours. This reaction is carried out under a mixed atmosphere of air / nitrogen, whereby the acid value is 100 mg.
A photocurable resin solution (A-2) having a KOH / g, a double bond equivalent of 450, and a weight average molecular weight of 14,000 was obtained.

Synthesis Example 4 250 g of propylene glycol monomethyl ether (manufactured by Daicel Chemical Industries, Ltd., MMPG) was introduced into a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube. After raising the temperature to 110 ° C, β-CEA (β-carboxyethyl acrylate) 26.3 g, methacrylic acid 141.2 g, methyl methacrylate 91.3 g, tetrahydrofurfuryl acrylate 39.0 g, MFDG 223 g, and t- 12.0 g of butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, Perbutyl O) was added dropwise over 3 hours. After dropping, a trunk polymer having a carboxyl group was synthesized by aging for 3 hours. Next, 202.2 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., Cyclomer A200), 2.0 g of triphenylphosphine, and 1.0 g of methylhydroquinone were added to the solution of the trunk polymer. The reaction was performed at 100 ° C. for 10 hours. This reaction is carried out in a mixed atmosphere of air / nitrogen, whereby an acid value of 10
A photocurable resin solution (A-2) having 0 mgKOH / g, a double bond equivalent of 450, and a weight average molecular weight of 13,500 was obtained.

Synthesis Example 5 (Synthesis of Photosensitive Prepolymer) 190 parts of a phenol novolak type epoxy compound (Epiclon N-770, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent = 190) was measured with a thermometer, a dropping funnel and a stirrer. The mixture was placed in a four-necked flask equipped with a reflux condenser, and 141 parts of carbitol acetate was added, followed by heating and dissolving. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 85 to 95 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted with stirring for 16 hours.
Active energy ray-curable resin (C) which is a total esterified product of 5% novolak type epoxy compound with acrylic acid
-1) was obtained.

Comparative Synthesis Example A cresol novolak-type epoxy resin (Nippon Kayaku Co., Ltd., E) was placed in a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube.
OCN-104S, softening point 92 ° C, epoxy equivalent 22
0) 660 g, carbitol acetate 421.3
g, and 180.6 g of solvent naphtha, and 9
The mixture was heated and stirred at 0 ° C. to dissolve. Next, the mixture was once cooled to 60 ° C., added with 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone, and allowed to react at 100 ° C. for 12 hours.
An OH / g reaction product was obtained. This was charged with 241.7 g of tetrahydrophthalic anhydride and heated to 90 ° C.
The reaction was carried out for an hour to obtain a resin solution having a solid content acid value of 80 mgKOH / g and a solid content concentration of 65%.

Examples 1 to 6 and Comparative Examples Using the resin solutions of Synthesis Examples 1 to 5 and Comparative Synthesis Examples thus obtained, the components other than the following components were mixed at the composition ratios shown in Table 1. Then, the mixture was preliminarily mixed with a stirrer and kneaded with a three-roll mill to prepare a photosensitive resin composition. Here, when the degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement using a grindmeter manufactured by Eriksen, it was 15 μm or less. In each of Examples and Comparative Examples, the curing agent component of the composition refers to the following epoxy compound (F) component, melamine, and the diluent component in Table 1, and the main component component refers to components other than these.

In addition to the components shown in Table 1, components contained in each of the compositions of Examples 1 to 6 and Comparative Example: [photopolymerization initiator (E)] 2-methyl [4- (methylthio) phenyl] -2 -Morpholino-1-propanone (Irgarcure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.): 5 parts Diethylthioxanthone (Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 0.5 parts [Epoxy Compound (F)] ・ Bixylenol type epoxy resin (YY-4000 manufactured by Yuka Shell Epoxy Co., Ltd.): 10 parts ・ Phenol novolak type epoxy resin component (Nippon Kayaku Co., Ltd., RE306): 3 parts [ Latent curing adhesion imparting agent (G)] Dicyandiamide (DICY): 0.2 part Melamine: 3 parts Inorganic filler (H) Barium sulfate: 6 parts Talc 4 parts Silica: 10 parts [Other Components] - antifoaming agent (manufactured by Kyoeisha Chemical Co., Ltd., Flowlen AC-300): 1 parts Phthalocyanine Green 0.3 part

[0053]

[Table 1]

Next, the photosensitive resin composition thus prepared was applied to the entire surface of the copper through-hole printed wiring board by screen printing, and the coating was applied at 80 ° C. for 20 minutes in a hot air circulating furnace. After drying, UV light having a wavelength of 365 nm was irradiated through a photomask at a light amount of 200 mJ / cm ² using an integrating luminometer manufactured by Oak Manufacturing Co., Ltd., and photo-cured, and then applied to a 1 wt% sodium carbonate developing solution. After developing at a spray pressure of 0.2 MPa for 60 seconds,
A solder resist pattern was formed by heat curing in a hot air circulation type curing furnace set at 150 ° C. for 60 minutes.

The following tests were performed on the various characteristics of the thus obtained photosensitive resin composition for solder resist and the solder resist pattern. Table 2 shows the evaluation results.

[Table 2]

As is clear from the results shown in Table 2 above,
The photosensitive resin composition according to the present invention has various properties required for a solder resist, that is, drying properties, dryness of a dry coating to the touch, thermosetting properties, and solder heat resistance of a cured film, solvent resistance, In addition to satisfying chemical resistance, adhesion, electrical insulation, electrolytic corrosion resistance, etc., light sensitivity and resolution can be dramatically improved,
In addition, it was confirmed that the electroless gold plating resistance was excellent. The test contents and evaluation methods shown in Table 2 are as follows.

(1) Drying to the touch after drying The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot-air circulation drying oven.
The test piece was dried for 10 minutes or 20 minutes using a test piece, and the coated surface was strongly pressed with a finger, and the adhesiveness was investigated to determine the state of the coating film. A: No stickiness or fingerprint mark was observed at all. ：: Slight stickiness and fingerprint marks are observed on the surface. Δ: Remarkable stickiness and fingerprint marks are observed on the surface. X: The surface is completely tacky.

(2) Hot tack-free property The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot-air circulation drying oven.
After drying for 15 minutes and allowing to cool,
The test piece was dried horizontally at 0 ° C for 20 minutes.
The state of the coating film was visually determined. ：: No scratches or dents were observed. ：: The surface is slightly scratched or dented. Δ: Notable scratches and dents are observed on the surface. ×: The surface is completely damaged.

(3) Developability Test The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot air circulation drying oven.
The test piece was dried for a predetermined time (60 to 90 minutes) as a test piece, developed with a developer having a spray pressure of 0.2 MPa for 60 seconds, and the state of removal of the coating film was visually determined. A: Completely developed. ：: There is a part which is not developed easily on the surface. Δ: Development residual as a whole. X: Hardly developed.

(4) Photosensitivity test The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot air circulation type drying furnace.
After drying for 20 minutes at a wavelength of 3
The 65nm UV using ORC Manufacturing Co., Ltd. integrated light intensity meter and irradiated with light intensity of 100 mJ / cm ² or 200 mJ / cm ^2, by developing for 60 seconds with a developer solution of a spray pressure 0.2MPa, respectively After that, the state of the coating film was visually determined. A: No change was observed. ：: The surface is slightly changed. Δ: The surface is significantly changed. ×: The coating film comes off.

(5) Adhesion test The photosensitive resin composition was applied to a copper through-etched circuit board by screen printing, and then heated to 80 ° C. using a hot-air circulation drying oven.
After drying for 20 minutes at a wavelength of 3
A test piece was irradiated with 65 nm ultraviolet light at a light amount of 350 mJ / cm ² using an integrating light meter manufactured by Oak Manufacturing Co., Ltd., and developed for 60 seconds with a developer at a spray pressure of 0.2 MPa. A test piece was prepared by post-curing at 150 ° C. for 60 minutes, and a cross cut in a grid pattern was made according to the test method of JIS D0202, and then a peeling test was performed using a cellophane adhesive tape.
The peeling state of the coating film was visually determined. A: 100/100 without any peeling. ：: The cross cut portion was slightly peeled off at 100/100. Δ: Peeled in the range of 50/100 to 90/100. ×: Peeled in the range of 0/100 to 50/100.

(6) Pencil hardness test Using the same test piece as in the adhesion test (5), the hardness was measured under a load of 1 kg in accordance with the test method of JIS K5400.

(7) Acid Resistance Test Using the same test piece as in the adhesion test (5), each was immersed in a 10% by volume aqueous sulfuric acid solution at 20 ° C. for 30 minutes and then taken out. Was evaluated. A: No change was observed. ：: slightly changed. Δ: Notably changed. X: The coating film has blisters or swelling and falling off.

(8) Alkali Resistance Test An acid resistance test was conducted and evaluated in the same manner as in the above acid resistance test (7), except that the 10% by volume aqueous sulfuric acid solution was replaced with a 10% by weight aqueous sodium hydroxide solution.

(9) Solvent Resistance Test Except that the 10% by volume sulfuric acid aqueous solution was replaced with acetone,
The test and evaluation were performed in the same manner as in the acid resistance test (7).

(10) Electroless Gold Plating Resistance Test The same test piece as in the adhesion test (5) was used at 75 ° C. with “AURED” (a plating solution manufactured by Kojima Chemical Co., Ltd.). The state of the coating film after plating at a temperature for 10 minutes to deposit gold having a thickness of 0.5 μm was evaluated in the same manner as in the acid resistance test (7).

(11) Solder heat resistance test Using the same test piece as in the adhesion test (5), the operation of dipping in a solder bath at 260 ° C. for 10 seconds was performed once and three times in accordance with the test method of JIS C6481. Thereafter, the state of the coating film was evaluated in the same manner as in the acid resistance test (7).

(12) Insulation Resistance Measurement A test piece was prepared using the comb test pattern B of IPC-B-25 under the same conditions as in the adhesion test (5).
Initial insulation resistance, relative temperature 85 ° C, relative humidity 85%,
The insulation resistance was measured after performing a humidification test for 500 hours under the condition of applying a direct current of 50 V.

(13) Electric corrosion resistance test A test piece was prepared using the comb test pattern B of IPC-B-25 under the same conditions as in the adhesion test (5).
A humidification test was performed for 500 hours under the conditions of a relative temperature of 85 ° C., a relative humidity of 85%, and a direct current of 50 V, and the discoloration of the copper foil after the test was investigated. A: No change was observed. ：: slightly changed. Δ: Notably changed. X: The coating film has blisters or swelling and falling off.

(14) Measurement of Resolution The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot-air circulation drying oven.
After drying for 20 minutes with a predetermined photomask (line 3)
0 μm to 100 μm), wavelength of 365 nm
The test piece was irradiated with ultraviolet light of 200 mJ / cm ² using an integrating luminometer manufactured by Oak Manufacturing Co., Ltd., and developed for 60 seconds with a developer having a spray pressure of 0.2 MPa. The state of remaining lines in the exposed area and the state of space removability were visually determined.

(15) Sensitivity Measurement The photosensitive resin composition is applied to a copper through-etched circuit board by screen printing, and is heated to 80 ° C. using a hot air circulation type drying furnace.
After drying for 20 minutes at a wavelength of 3
A test piece was irradiated with an ultraviolet light of 65 nm at a light amount of 200 mJ / cm ² using an integrating light meter manufactured by Oak Manufacturing Co., Ltd., and was developed for 60 seconds with a developing solution at a spray pressure of 0.2 MPa. The number of steps of the remaining coating film was visually determined. The photomask is made by Eastman Kodak,
Step tablet No. 2 was used.

[0072]

As described above, according to the photosensitive resin composition of the present invention, various characteristics required for a solder resist can be satisfied, and the photosensitivity and resolution can be significantly improved. A solder resist particularly excellent in electrolytic gold plating resistance can be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/46 C08F 2/46 290/04 290/04 299/02 299/02 G03F 7/004 501 G03F 7 / 004 501 F-term (reference) 2H025 AA01 AA02 AB15 AC01 AD01 BC34 BC52 BC53 BC66 BC73 BC74 BC82 BC84 CA00 CC06 CC08 CC17 4J011 AA05 PA04 PA07 PA09 PA13 PA36 PA43 PA45 PA46 PA47 PA48 PA65 PA70 PB22 PB39 QA03 QA37 QA Q19 SA31 SA51 SA61 SA63 SA64 SA79 SA83 WA01 4J027 AA01 AA02 AE03 AE07 BA07 BA13 CA02 CA10 CA14 CA16 CA18 CA23 CA25 CA26 CA27 CA31 CA36 CD10

Claims (8)

[Claims] 1. (A-1) (a) β-carboxyethyl acrylate, (b) an acid group-containing unsaturated compound, and (c)
(B) acetoacetoxyethyl acrylate, a modified copolymer obtained by adding an epoxy group of an alicyclic epoxy group-containing unsaturated compound to a part of acid groups of a copolymer composed of a (meth) acrylate ester, (C) at least one monomer selected from the group consisting of acryloylmorpholine and tetrahydrofurfuryl acrylate, (C) an active energy ray-curable resin having two or more unsaturated groups in one molecule and having a cyclic skeleton, A photosensitive resin composition comprising: D) a diluent; and (E) a photopolymerization initiator. 2. (A-2) (a) β-carboxyethyl acrylate, (b) an acid group-containing unsaturated compound, (c)
(D) a part of an acid group of a copolymer comprising at least one monomer selected from the group consisting of (meth) acrylic acid ester and (d) acetoacetoxyethyl acrylate, acryloylmorpholine and tetrahydrofurfuryl acrylate; A modified copolymer obtained by adding an epoxy group of an unsaturated compound having the formula epoxy group, (C) 1
An active energy ray-curable resin having at least two unsaturated groups in the molecule and having a cyclic skeleton, (D) a diluent, and (E)
A photosensitive resin composition comprising a photopolymerization initiator. 3. An active energy ray-curable resin (C) comprising:
A photosensitive prepolymer (C-) which is an esterified product of an epoxy group formed by an esterification reaction between (e) a novolak type epoxy compound and (f) an unsaturated monocarboxylic acid.
Reacting a reaction product of 1) and (g) a diisocyanate with (h) a (meth) acrylate having one hydroxyl group in one molecule with a secondary hydroxyl group of the photosensitive prepolymer (C-1); The photosensitive prepolymer (C-
2) at least one selected from the group consisting of:
The compounding ratio of the component (A) and the component (C) is 100: 2 to 10
0:50 (based on mass).
Or the photosensitive resin composition according to 2. 4. The photosensitive resin composition according to claim 1, further comprising (F) an epoxy compound. 5. The photosensitive resin composition according to claim 1, further comprising (G) a latent curing adhesion-imparting agent. 6. The photosensitive resin composition according to claim 1, further comprising (H) an inorganic filler. 7. The photosensitive resin composition according to claim 1, wherein the alicyclic epoxy group-containing unsaturated compound is 3,4-cyclohexylmethyl (meth) acrylate. object. 8. The photosensitive resin composition according to claim 1, which is used as a solder resist, an etching resist, an interlayer insulating material, a plating resist, or an FPD member.