JP2000355621A - Photosensitive resin composition and its cured item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in developability and photosensitivity and gives a cured item excellent in adhesive properties, pencil hardness, resistances to solvents, acids, heat, and gold plating, etc. SOLUTION: This composition comprises (A) an unsaturated polycarboxylic acid resin, (B) a crosslinker, (C) a photopolymerization initiator, and (D) a curing component provided that the unsaturated polycarboxylic acid resin A comprises (A-1) an unsaturated polycarboxylic acid resin which is a reaction product of a reaction product of (a-1) a polyepoxy compound having an epoxy equivalent of 280-500 g/eq with (b) an unsaturated monocarboxylic acid with (c) a polybasic acid anhydride and (A-2) an unsaturated polycarboxylic acid resin which is a reaction product of a reaction product of (a-2) a polyepoxy compound having an epoxy equivalent of 150-230 g/eq with an unsaturated monocarboxylic acid with a polybasic acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a cured product, and more particularly to a photosensitive resin composition useful for manufacturing a printed circuit board and suitable for a liquid solder resist which can be developed with an aqueous alkali solution.

[0002]

2. Description of the Related Art In the printed circuit board manufacturing industry, a solder resist is widely used as a permanent protective film for a printed circuit board. The solder resist is used for the purpose of preventing a solder bridge at the time of soldering, preventing corrosion of a conductor portion at the time of use, maintaining electrical insulation, and the like. Conventionally, a method of forming a solder resist by screen printing using a thermosetting ink or a photocurable ink has been widely used. However, when this method is used, bleeding, bleeding, sagging, and the like at the time of printing reduce the accuracy of the obtained resist pattern, and can respond to recent miniaturization, high density, and high functionality of printed circuit boards. It's gone.

In order to cope with such a printed circuit board, many photo-curable liquid solder resists have been developed, and 50% or more are currently introduced. Among them, those which can be developed with an alkaline aqueous solution have attracted attention, and are characterized by containing a resin having a carboxyl group for dissolving in an alkaline aqueous solution and an ethylenically unsaturated group for imparting photocurability as an essential component. . For example, Japanese Patent Application Laid-Open
No. 62375, JP-A-3-253093 and JP-B-1-54390 disclose phenolic or o-
A resist composition using a resin obtained by reacting a cresolic novolak type epoxy resin with an unsaturated monobasic acid and further reacting a saturated or unsaturated polybasic acid anhydride is disclosed. JP-A-3-289656 discloses that glycidyl (meth) acrylate and the like are copolymerized as constituents,
A composition using a resin in which an epoxy group is modified in the same manner as the above-mentioned resin, and JP-A-2-97513 discloses an epoxy compound of a condensate of phenols and an aromatic aldehyde having a phenolic hydroxyl group, A) A composition using an ethylenically unsaturated group-containing polycarboxylic acid resin obtained by reacting a reaction product with acrylic acid with a polybasic carboxylic acid or an anhydride thereof is disclosed.

[0004]

However, when these compositions are used, for example, as a resin composition for a solder resist, they are excellent in sensitivity, resolution, heat resistance, etc., but have an excellent cured film resistance. There is a problem that the chemical property, the gold plating resistance, and the electrolytic corrosion resistance are insufficient, and cracks are generated on the surface of the cured product. Further, when a thinned substrate is used, a problem that the substrate is warped may occur.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, they have shown high sensitivity and high resolution, and can be developed with a dilute alkaline aqueous solution. The printed circuit board also has excellent solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, etc., does not crack on the cured product surface, and does not warp even when a thinned substrate is used. A photosensitive resin composition for use as well as a cured product have been found. That is, the present invention provides (1) an unsaturated group-containing polycarboxylic acid resin (A), a crosslinking agent (B), and a photopolymerization initiator (C).
And a photosensitive resin composition containing a curing component (D), wherein the unsaturated group-containing polycarboxylic acid resin (A) contains 2
Having at least 280 epoxy groups and an epoxy equivalent of 280
Unsaturated group-containing polycarboxylic acid resin which is a reaction product of an epoxy resin (a-1) with an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c) in an amount of from 500 g / equivalent. (A-1) and an epoxy resin (a-2) having two or more epoxy groups in a molecule and having an epoxy equivalent of 150 to 230 g / equivalent, and an unsaturated group-containing monocarboxylic acid (b). A photosensitive resin composition comprising, simultaneously, an unsaturated group-containing polycarboxylic acid resin (A-2) which is a reaction product of a reactant and a polybasic acid anhydride (c);

(2) Reaction between an epoxy resin (a-1) having two or more epoxy groups in the molecule and having an epoxy equivalent of 280 to 500 g / equivalent and an unsaturated group-containing monocarboxylic acid (b) X is the solid weight of the unsaturated group-containing polycarboxylic acid resin (A-1), which is a reaction product of the product and the polybasic acid anhydride (c), having two or more epoxy groups in the molecule, and Unsaturated group-containing polycarboxylic acid resin (A-2) which is a reaction product of an epoxy resin (b) having an epoxy equivalent of 150 to 230 g / equivalent and an unsaturated group-containing monocarboxylic acid and a polybasic anhydride. )), X / X
The photosensitive resin composition according to (1), wherein the value of Y is an unsaturated group-containing polycarboxylic acid resin (A) having 0.25 or more and 4 or less, (3) an unsaturated group-containing polycarboxylic acid resin ( A),
Crosslinking agent (B), photopolymerization initiator (C) and curing component (D)
Wherein the unsaturated group-containing polycarboxylic acid resin (A) has two or more epoxy groups in the molecule and has an epoxy equivalent of 280 to 500 g / equivalent. 1) and having two or more epoxy groups in the molecule, and having an epoxy equivalent of 150 to 230 g /
Unsaturated group-containing product which is a reaction product of an epoxy resin which is a mixture with an equivalent amount of epoxy resin (a-2), an unsaturated group-containing monocarboxylic acid (b), and a polybasic anhydride (c) A photosensitive resin composition, which is a polycarboxylic acid resin (A-3);

(4) The epoxy resin (a-1) having two or more epoxy groups in the molecule and having an epoxy equivalent of 280 to 500 g / equivalent has a solid weight of L, and two or more epoxy resins in the molecule. An epoxy group having an epoxy equivalent of 150 to 2;
When the solid content weight of the epoxy resin (a-2) at 30 g / equivalent is defined as M, the mixture of the epoxy resin having an L / M value of 0.11 or more and 9 or less and the unsaturated group-containing monocarboxylic acid (b The photosensitive resin composition according to (3), which is an unsaturated group-containing polycarboxylic acid resin (A-3), which is a reaction product of (a) with the polybasic acid anhydride (c); It has two or more epoxy groups in the molecule and has an epoxy equivalent of 280
The photosensitive resin composition according to any one of (1) to (4), wherein 500 g / equivalent of the epoxy resin (a-1) is a reaction product of a bisphenol-type epoxy resin and epihalohydrin; The epoxy resin (a-2) having two or more epoxy groups therein and having an epoxy equivalent of 150 to 230 g / equivalent is a novolak-type epoxy resin or an epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde. (1) The photosensitive resin composition according to any one of (4) to (4),

(7) Unsaturated group-containing monocarboxylic acid (b)
Is (meth) acrylic acid, the photosensitive resin composition according to any one of (1) to (6), (8) the polybasic anhydride (c) is maleic anhydride, succinic anhydride, (9) The photosensitive resin composition according to any one of (1) to (7), which is a polybasic anhydride selected from phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Polycarboxylic acid resin containing unsaturated group (A)
The photosensitive resin composition according to any one of (1) to (8), wherein the solid content acid value of the photosensitive resin is in the range of 50 to 150 mg · KOH / g, and (10) the crosslinking agent (B) is (meth) (1) The photosensitive resin composition according to any one of (1) to (9), which is an acrylate compound, and (11) an epoxy resin in which the curing component (D) is dissolved in an acetate-based solvent at room temperature. Or the photosensitive resin composition according to any one of (11) to (12), wherein the curing component (D) is a novolak epoxy resin, a bisphenol epoxy resin, or an epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde. And epoxy resins selected from among naphthalene skeleton-containing epoxy resins (1) to (11).
The photosensitive resin composition according to any one of the above, (13)
The present invention relates to a cured product of the photosensitive resin composition according to any one of (1) to (12), and a printed board having a layer of the cured product according to (14) or (13).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention comprises an unsaturated group-containing polycarboxylic acid resin (A), a crosslinking agent (B),
It comprises a photopolymerization initiator (C) and a curing component (D). The term "photosensitivity" as used herein refers to a property of being polymerized and cured in the presence or absence of a photopolymerization initiator (C) by irradiation with an energy beam such as an electron beam or ultraviolet light.

The photosensitive resin composition of the present invention uses a specific unsaturated group-containing polycarboxylic acid resin (A), and has two modes. In the first mode, the unsaturated group-containing polycarboxylic acid resin (A) has two or more epoxy groups in a molecule and has an epoxy equivalent of 280 to 50.
Reaction product of 0 g / equivalent of epoxy resin (a-1) with unsaturated group-containing monocarboxylic acid (b) and polybasic acid anhydride (c)
With unsaturated group-containing polycarboxylic acid resin (A)
-1) and a reaction product of an epoxy resin (a-2) having two or more epoxy groups in a molecule and having an epoxy equivalent of 150 to 230 g / equivalent, and an unsaturated group-containing monocarboxylic acid (b) And an unsaturated group-containing polycarboxylic acid resin (A-2) which is a reaction product of a polybasic acid anhydride and an unsaturated group-containing polycarboxylic acid resin (A-1). X) and the solid content weight of the unsaturated group-containing polycarboxylic acid resin (A-2) as X, X /
The value of Y is preferably 0.25 or more and 4 or less and is an unsaturated group-containing polycarboxylic acid resin (A). If the amount deviates from this range, the developability deteriorates, and there are problems such as remaining on the substrate as a residue after development and problems such as cracks occurring on the surface of the cured product.

In a second embodiment, the unsaturated group-containing polycarboxylic acid resin (A) has two or more epoxy groups in the molecule and has an epoxy equivalent of 280 to 500 g / equivalent. 1) and an epoxy resin which is a mixture of an epoxy resin (a-2) having two or more epoxy groups in a molecule and having an epoxy equivalent of 150 to 230 g / equivalent, and an unsaturated group-containing monocarboxylic acid ( b) using the unsaturated group-containing polycarboxylic acid resin (A-3), which is a reaction product of the reaction product with the polybasic acid anhydride (c), and the solid content of the epoxy resin (a-1). When the weight per minute is L and the weight of the solid content of the epoxy resin (a-2) is M, it is preferable that the value of L / M is a mixture of epoxy resins of 0.11 or more and 9 or less. If the amount deviates from this range, the developability deteriorates, and there are problems such as remaining on the substrate as a residue after development and problems such as cracks occurring on the surface of the cured product.

As the epoxy resin (a-1) having two or more epoxy groups in the molecule and having an epoxy equivalent of 280 to 500 g / equivalent, an alcoholic hydroxyl group of a bisphenol-type epoxy resin may be further substituted with epihalohydrin such as epichlorohydrin. The glycidylated reactant is preferred.
The reaction product can be obtained, for example, by reacting an alcoholic hydroxy group of a bisphenol-type epoxy resin with an epihalohydrin such as epichlorohydrin, preferably in the presence of dimethyl sulfoxide. Epihalohydrin may be used in an amount of 1 equivalent or more based on 1 equivalent of the alcoholic hydroxy group. However, use of more than 15 equivalents to 1 equivalent of the alcoholic hydroxyl group is not preferable because the effect of increasing the amount hardly occurs and the volumetric efficiency also decreases.

When dimethyl sulfoxide is used, the amount of dimethyl sulfoxide used is 5 to 3 with respect to the bisphenol type epoxy resin.
00% by weight is preferred. If this amount is less than 5% by weight,
The reaction between the alcoholic hydroxy group and the epihalohydrin in the bisphenol-type epoxy resin is slowed, and a long-time reaction is required. On the other hand, if it exceeds 300% by weight, the effect of increasing the amount is almost lost and the volumetric efficiency is undesirably reduced.

In carrying out the reaction, an alkali metal hydroxide is used. As the alkali metal hydroxide, for example, sodium hydroxide, potassium hydroxide and the like can be used, but sodium hydroxide is preferable. The amount of the alkali metal hydroxide used may be excessive if the total amount of alcoholic hydroxy groups is to be epoxidized, but if it is used in excess of 2 equivalents relative to 1 equivalent of alcoholic hydroxy groups, Tend to occur.

The alkali metal hydroxide may be used in the form of a solid or an aqueous solution. The reaction temperature is 30 to 1
00 ° C is preferred. When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. On the other hand, when it exceeds 100 ° C., many side reactions occur, which is not preferable.

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), bisphenol such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei) An epoxy resin (a-1) which is a reaction product of these resins with epihalohydrin is manufactured by Nippon Kayaku Co., Ltd. as NER-1000 series and NER-7000 series, for example. ing.

The epoxy resin (a-2) having two or more epoxy groups in the molecule and having an epoxy equivalent of 150 to 230 g / equivalent includes, for example, a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. Novolak type epoxy resin and epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

As an epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde, for example, EPPN-
502H, EPPN-503 (all manufactured by Nippon Kayaku),
TACTICX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (Yukaka Epoxy Co., Ltd.)
Manufactured).

Examples of the unsaturated group-containing monocarboxylic acid (b) used in synthesizing the polycarboxylic acid resin (A) used in the present invention include (meth) acrylic acid,
Cinnamic acid, cyanocinnamic acid, etc., and these unsaturated group-containing monocarboxylic acids (b) can be used alone or in combination of two or more, but they increase photosensitivity and easily increase crosslinkability. Particularly preferred is (meth) acrylic acid.

The rate of addition of these unsaturated group-containing monocarboxylic acids (b) is such that when the unsaturated group-containing polycarboxylic acid resin (A) is synthesized separately from each epoxy resin, the epoxy equivalent is 280 to 500 g / equivalent. It is preferable that the epoxy resin (a) has an epoxy equivalent of 70 to 120 mol% of the epoxy equivalent of the epoxy resin (b) having an epoxy equivalent of 150 to 230 g / equivalent. If the addition ratio is less than 70 mol%, the photosensitivity is insufficient, and
When the content is 20 mol% or more, unreacted unsaturated group-containing monocarboxylic acid (b) is not preferred because it may cause problems such as a decrease in adhesion of a cured product.

The unsaturated group-containing polycarboxylic acid resin (A) is prepared by mixing an epoxy resin (a-1) having an epoxy equivalent of 280 to 500 g / equivalent, and an epoxy resin having an epoxy equivalent of 150 to 23.
When synthesizing from an epoxy resin which is a mixture with 0 g / equivalent of epoxy resin (a-2), it has two or more epoxy groups in a molecule and an epoxy equivalent of 280 to 500 g.
Epoxy resin (a-1) having a solid weight of L, an epoxy equivalent of wpe1, an epoxy equivalent having two or more epoxy groups in the molecule, and an epoxy equivalent of 150 to 230 g / equivalent. Assuming that the solid content weight of 2) is M and the epoxy equivalent is wpe2, the average epoxy equivalent wpe of the epoxy resin mixture is calculated by the following equation 1, and the average epoxy equivalent wpe is 70 to 120 mol% of the unsaturated group-containing monocarboxylic acid. Preferably, the acid (b) is reacted. Deviations from this amount can cause similar problems as described above. wpe

[0023]

Formula 1 wpe = (L + M) / ((1 / wpe1) * L + (1 / wpe2) * M) Formula 1

The reaction of the epoxy resin (a-1) or the epoxy resin (a-2) or a mixture thereof with the unsaturated group-containing monocarboxylic acid (b) uses a catalyst to promote the reaction. The amount of the catalyst is preferably 0.1 to 10% by weight based on the reaction raw material mixture. In order to prevent thermal polymerization during the reaction, it is preferable to use a thermal polymerization inhibitor, and the amount used is preferably 0.01 to 1% by weight based on the reaction raw material mixture. At that time, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, octane Zirconium acid and the like. Examples of the thermal polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, tert-butylcatechol, pyrogallol and the like.

The polybasic acid anhydride (c) used in synthesizing the unsaturated group-containing polycarboxylic acid resin (A) of the present invention.
Examples thereof include one or more polybasic acid anhydrides selected from maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. These polybasic acid anhydrides (c)
Can be used alone or in combination of two or more.
The polybasic acid anhydride (c) is prepared by using the epoxy resin (a-
1) or an epoxy resin (a-2) or a mixture of these epoxy resins and an unsaturated group-containing monocarboxylic acid (b), which is half-esterified by addition to a hydroxy group produced or introduced to form a carboxylic acid. Generate The generated carboxylic acid is indispensable for imparting developability to an aqueous alkali solution, and the acid value of the solid content of the unsaturated group-containing polycarboxylic acid resin (A) of the present invention is:
It is preferable that the amount be 50 to 150 mg · KOH / g. When the acid value of the solid content is less than 50 mg · KOH / g, the developability of the resin composition described later in an aqueous alkaline solution is significantly reduced, and in the worst case, development becomes impossible, which is not preferable. On the other hand, when the acid value of the solid content exceeds 150 mg · KOH / g, the developability of the aqueous alkali solution is too high, and the adhesion to development may be reduced, or in the worst case, a pattern may not be obtained.

As a method of reacting the polybasic acid anhydride (c), the polybasic acid anhydride (c) is added to the reaction product of the epoxy resin and the unsaturated group-containing monocarboxylic acid to obtain the solid content acid value described above. At a reaction temperature of 60 to 150 ° C, 5 to 6
It can be obtained by reacting for 0 hours. In order to prevent thermal polymerization during the reaction, it is preferable to use a thermal polymerization inhibitor, and the amount used is preferably 0.01 to 1% by weight based on the reaction raw material mixture. As the thermal polymerization inhibitor, those described above can be used.

The amount of the unsaturated group-containing polycarboxylic acid resin (A) used in the photosensitive resin composition of the present invention is 10 to 10% when the total solid content of the photosensitive resin composition is 100% by weight. It is preferably 80% by weight, particularly preferably 1% by weight.
5 to 70% by weight.

The crosslinking agent (B) used in the photosensitive resin composition of the present invention includes (meth) acrylate compounds, azide compounds, diazo compounds, nitro compounds and the like. (Meth) acrylate compounds which can be radically polymerized by C) and can easily undergo a crosslinking reaction with the unsaturated group-containing polycarboxylic acid resin (A) are particularly preferred. As the (meth) acrylate compound,
For example, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, acryloyl monophorin, isobornyl (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane Tetra (meta)
Acrylates such as acrylate and dipentaerythritol poly (meth) acrylate can be exemplified. These can be used alone or in combination.

The amount of the crosslinking agent (B) used in the photosensitive resin composition of the present invention is preferably from 1 to 40% by weight when the total solid content of the photosensitive resin composition is 100% by weight. Particularly preferably, it is 5 to 30% by weight.

The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention includes, for example, acetophenone,
2,2-diethoxy-2-phenylacetophenone, p
-Dimethylaminopropiophenone, dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Benzophenones such as acetophenones such as phenyl) -butanone-1, benzophenone, p-chlorobenzophenone, p, p-bisdimethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, and 4-benzoyl-4'-methyl-diphenylsulfide Benzoin ethers such as benzyl, benzoin, benzoin methyl ether and benzoin isobutyl ether; ketals such as benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and 2-iso Thioxanthones such as propylthioxanthone, anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide And the like. These photopolymerization initiators (C) may be used alone or
More than one species can be used in combination. The amount used is preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight in the composition.

These photopolymerization initiators (C) include, for example, N, N-dimethylaminobenzoic acid ethyl ester, N, N
N-dimethylaminobenzoic acid isoamyl ester, N,
Pentyl N-dimethylaminobenzoate, 4,
It can be used in combination with a sensitizer such as 4'-bis (N, N-dimethylamino) -benzophenone and 4,4'-bis (N, N-dimethylamino) -benzophenone. As the amount of the sensitizer, the photopolymerization initiator (C)
Is preferably 50% by weight or less.

The curing component (D) used in the present invention comprises:
It reacts thermally with the carboxyl group in the unsaturated group-containing polycarboxylic acid resin (A) during heat curing after development to impart alkali resistance, solvent resistance, heat resistance and electrical insulation to the cured coating film. However, an epoxy resin which is soluble in an acetate-based solvent at room temperature and which can enhance the resolution of a transfer pattern, have good development adhesion, and enhance the gold plating resistance of a cured film is particularly preferable. When an epoxy resin that is hardly soluble in an acetate solvent at room temperature is used, there is a risk that the composition will be left as crystals when left unattended, or the development margin is small, and when trying to transfer a fine pattern, an inverted trapezoidal shape is used. It becomes a pattern and may peel off in the worst case.

Examples of the curing component (D) soluble in an acetate solvent at room temperature include novolak type epoxy resin, bisphenol type epoxy resin, epoxy resin of polycondensate of phenol and hydroxybenzaldehyde, and epoxy resin containing naphthalene skeleton. No.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

As an epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde, for example, EPPN-
502H, EPPN-503 (all manufactured by Nippon Kayaku),
TACTICX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (Yukaka Epoxy Co., Ltd.)
Manufactured).

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), bisphenol such as UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei) F-type epoxy resins and the like can be mentioned.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.). As the alicyclic epoxy resin, for example, EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.).

These curing components (D) can be used alone or
More than one species can be used in combination. The amount used is preferably from 1 to 50% by weight, particularly preferably from 3 to 45% by weight in the composition.

Further, these curing components (D) include:
In order to further improve properties such as adhesion, chemical resistance, and heat resistance, it is particularly preferable to use an epoxy resin curing (acceleration) agent in combination. The amount of epoxy resin curing (acceleration) agent used is
0.01 to 100 parts by weight of the epoxy compound
The amount is preferably 25 parts by weight, particularly preferably 0.1 to 15 parts by weight. Commercially available products include, for example, C11Z, 2PH
Z, 2MZ-AZINE, 2E4MZ-AZINE, 2
Imidazole and its derivatives such as E4MZ-CN and 2MA-OK (all manufactured by Shikoku Chemical Industry Co., Ltd.), and tertiary amines such as hexa (N-methyl) melamine and 2,4,6-tris (dimethylamino) phenol Compounds, triazine compounds such as benzoguanamine, acetoguanamine and melamine, and acid anhydrides such as 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride And polyamines such as dicyandiamide and organic phosphines such as triphenylphosphine. Of these, melamine and dicyandiamide are preferred.

The photosensitive resin composition of the present invention may further comprise, if necessary, for the purpose of improving properties such as adhesion and hardness.
Inorganic fillers such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder can be used.
The amount used is preferably 60% by weight or less in the composition of the present invention, and particularly preferably 5 to 40% by weight.

Further, if necessary, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, and polymerization inhibition of hydroquinone, hydroquinone monomethyl ether, etc. Agents, thickeners such as asbestos, benton, montmorillonite, etc., adhesion-imparting agents such as silicone-based, fluoropolymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, etc. Additives such as agents can be used.

The photosensitive resin composition of the present invention comprises (A)
The components (B), (C), and (D), and if necessary, the inorganic filler and the other components described above are preferably mixed in the above-described ratio, and uniformly mixed, dissolved, and dispersed by a roll mill or the like. It can be obtained by: In addition, a solvent may be used together if desired, mainly for adjusting the viscosity. This solvent may be a solvent used in the production of the components. Examples of the solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, ethyl acetate, and acetic acid. Esters such as butyl, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. γ-butyrolactone, N-methyl-2-pyrrolidone, etc. Organic solvents.

When the above-mentioned curing component (D) and a curing accelerator are mixed in advance with a solder resist composition to form a one-pack type, the viscosity tends to increase before application to a circuit board blank. The two-component type is composed of a base solution containing the unsaturated group-containing polycarboxylic acid resin (A) as a main component and a curing accelerator and the like, and a curing agent solution containing the curing component (D) as a main component ( The components (B) and (C) are added to one or both of them), and it is preferable to use them in a mixture at the time of use.

The photosensitive resin composition of the present invention is useful in liquid form as a resist ink, particularly a resist ink for printed circuit boards, and can also be used as a paint, coating agent, adhesive or the like.

The cured product of the present invention is obtained by photo-curing the above-mentioned photosensitive resin composition of the present invention by irradiation with energy rays such as ultraviolet rays, and further obtained by further thermosetting the photo-cured cured film. is there. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. When irradiating ultraviolet rays, an ultraviolet ray generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and an ultraviolet light emitting laser (for example, an excimer laser) may be used. The cured product of the resin composition of the present invention is used for an electric / electronic component such as a printed board having a through hole as a permanent resist, for example.

The printed board of the present invention has a cured product layer of the above resin composition. The thickness of this cured product layer is 5 to 16
It is about 0 μm, preferably about 10 to 60 μm. The printed circuit board can be obtained, for example, as follows. That is, when a liquid resin composition is used, the printed wiring board is screen-printed, sprayed, roll-coated, electrostatically coated, curtain-coated, etc.
The composition of the present invention was applied to a thickness of 160 μm,
After drying at 0 to 110 ° C., the negative film is brought into direct contact with the coating film (or placed on the coating film in a non-contact state), irradiated with ultraviolet light, and the unexposed portion is diluted with a diluted alkaline aqueous solution described below. For example, development is performed by spraying, rocking immersion, brushing, scrubbing, or the like. Thereafter, the substrate is irradiated with ultraviolet rays as required, and then subjected to a heat treatment at 100 to 200 ° C., thereby obtaining a printed circuit board having a permanent protective film satisfying various characteristics.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Aqueous solutions of inorganic salts such as sodium bicarbonate, potassium bicarbonate, sodium metasilicate and potassium metasilicate; aqueous solutions of organic amines such as trimethylamine, triethylamine, monomethanolamine, diethanolamine and triethanolamine; tetramethylammonium hydroxide; Examples include ammonium hydroxide such as tetraethylammonium hydroxide. These can be used alone or in combination of two or more. The temperature is 15
It can be arbitrarily adjusted between -45 ° C. A small amount of a surfactant, an antifoaming agent or the like may be mixed in this developer.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto.

Synthesis Example 1 (Synthesis of Polycarboxylic Acid Resin Containing Unsaturated Group (A-1)) 118.44 g of carbitol acetate as a reaction solvent in a 2 liter flask having two or more epoxy groups in the molecule. NER-7403 as an epoxy resin (a-1) having an epoxy equivalent of 280 to 500 g / equivalent.
(Nippon Kayaku epoxy resin, reaction product of bisphenol-F type epoxy resin and epichlorohydrin epoxy equivalent:
291.4 g / 297.8 g / equivalent) and 92.30 g of acrylic acid as the unsaturated group-containing monocarboxylic acid (b).
g, 0.30 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.78 g of triphenylphosphine as a reaction catalyst, and reacted at a temperature of 98 ° C. for 24 hours. After completion of the reaction, 231.56 g of carbitol acetate, 176.26 g of tetrahydrophthalic anhydride as polybasic anhydride (c), and 0.38 g of 2-methylhydroquinone as a thermal polymerization inhibitor were charged into the solution at 95 ° C.
For 4 hours to obtain an unsaturated group-containing polycarboxylic acid resin solution (referred to as A-1-1). The concentration of the resin solution is about 65%, and the acid value of the solid content is 100 mg · KOH / g
Met.

Synthesis Example 2 (Synthesis of Polycarboxylic Acid Resin Containing Unsaturated Group (A-2)) 118.44 g of carbitol acetate as a reaction solvent in a 2 liter flask having two or more epoxy groups in the molecule. EPPN-503 as an epoxy resin (a-2) having an epoxy equivalent of 150 to 230 g / equivalent.
(Nippon Kayaku epoxy resin, epoxy resin epoxy equivalent of polycondensate of phenol and hydroxybenzaldehyde: epoxy equivalent: 180.0 g / equivalent) 338.30 g, and acrylic acid as unsaturated group-containing monocarboxylic acid (b): 135.30 g
44 g, 0.30 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.78 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. for 5 hours. After the reaction, 17.63 g of tetrahydrophthalic anhydride was added as polybasic acid anhydride (c), and the reaction was further continued at a temperature of 98 ° C. for 20 hours. After the reaction was completed, 231.56 g of carbitol acetate, 158.63 g of tetrahydrophthalic anhydride were added to this solution, and 2-hydrogen was used as a thermal polymerization inhibitor.
0.38 g of methylhydroquinone was charged and reacted at a temperature of 95 ° C. for 4 hours to obtain an unsaturated group-containing polycarboxylic acid resin solution (referred to as A-2-1). The concentration of the resin solution is about 65
% And the solid content acid value was 100 mg · KOH / g.

Synthesis Example 3 (Synthesis of Polycarboxylic Acid Resin Containing Unsaturated Group (A-3)) 118.44 g of carbitol acetate as a reaction solvent in a 2 liter flask having two or more epoxy groups in the molecule. NER-7403 as an epoxy resin (a-1) having an epoxy equivalent of 280 to 500 g / equivalent.
(Nippon Kayaku epoxy resin, reaction product of bisphenol-F type epoxy resin and epichlorohydrin epoxy equivalent:
297.8 g / equivalent) to 138.44 g, having two or more epoxy groups in the molecule, and having an epoxy equivalent of 150 to
As an epoxy resin (a-2) of 230 g / equivalent, EP
PN-503 (Nippon Kayaku epoxy resin, epoxy resin of polycondensate of phenol and hydroxybenzaldehyde, epoxy equivalent: 180.0 g / equivalent) was 215.52.
g (average epoxy equivalent of mixed epoxy resin of epoxy resin (a) and epoxy resin (b): 212.94 g / equivalent), 119.78 g of acrylic acid as unsaturated group-containing monocarboxylic acid (b), thermal polymerization 0.30 g of 2-methylhydroquinone as an inhibitor and 1.78 g of triphenylphosphine as a reaction catalyst were charged.
The reaction was performed for 4 hours. After completion of the reaction, 231.56 g of carbitol acetate was added to this solution, and polybasic acid anhydride (c)
176.26 g of tetrahydrophthalic anhydride, and 0.38 of 2-methylhydroquinone as a thermal polymerization inhibitor
g The mixture was reacted at a temperature of 95 ° C for 4 hours to obtain an unsaturated group-containing polycarboxylic acid resin solution (referred to as A-3-1). The concentration of the resin solution is about 65% and the acid value of the solid content is 100 m
g · KOH / g.

Examples 1 and 2 and Comparative Examples 1 and 2 Each component was blended according to the blending composition shown in Table 1 (the numerical values are parts by weight) and kneaded with a three-roll mill to prepare a photosensitive resin composition. This is screen-printed by 100
Using a mesh screen, apply the entire surface to a copper-clad glass epoxy substrate (thickness: about 0.5 mm) which is patterned to a thickness of 15 to 25 μm.
Dry for 30 minutes with a hot air dryer. Then, a negative film having a resist pattern is brought into close contact with the coating film, and an ultraviolet exposure apparatus (Oak Co., Ltd., model HMW-680G)
W) was used to irradiate ultraviolet rays (exposure amount: 200 mJ /
cm2). Next, development was performed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² to remove and remove unexposed portions. The obtained product was evaluated for developability, resolution, photosensitivity, and surface gloss as described below. Thereafter, heat curing was performed for 60 minutes in a hot air dryer at 150 ° C., and the test piece having the obtained cured film was subjected to substrate warpage, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and heat resistance as described below. A gold plating test was performed. Table 2 shows the results. In addition, the test method and the evaluation method are as follows.

(Developability) The following evaluation criteria were used.・ ・ ・: At the time of development, the ink was completely removed and development was possible. ×: Some parts are not developed during development.

(Resolution) A 50 μm negative pattern is adhered to the dried coating film, and the coated film is irradiated with ultraviolet rays having an integrated light amount of 200 mJ / cm ² . Next, it is developed with a 1% 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. The following criteria were used:・ ・ ・: The pattern edge is a straight line and is resolved. ×: peeling or pattern edges are jagged.

(Photosensitivity) A step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film, and the integrated light amount was 50
Irradiation exposure with ultraviolet rays of 0 mJ / cm ² is performed. Next, the film is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of steps of the coating film left undeveloped is confirmed. The following criteria were used: ○ ・ ・ ・ ・ 8 steps or more × ・ ・ ・ ・ 7 steps or less

(Surface gloss) After drying, the coating
/ Cm ² UV irradiation. Next, it is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the cured film after drying is observed. The following criteria were used: ○ ・ ・ ・ ・ No fogging is observed × ・ ・ ・ ・ Slight fogging is observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ ・ Warpage is not seen on the substrate × ・ ・ ・ ・ Warpage is seen on the substrate

(Adhesion) According to JIS K5400,
One hundred squares of 1 mm were formed on the test piece, and a peeling test was performed using cellophane tape. The state of peeling was evaluated by the following criteria. ○ ・ ・ ・ ・ No peeling ×× ・ Peel off

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

(Solvent resistance) A test piece is immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there was no abnormality in the appearance, a peeling test was carried out using cellophane tape and evaluated according to the following criteria. ○ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling ×× ・ ・ Film with blistering or peeling in the coating film

(Acid Resistance) A test piece is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there is no abnormality in the appearance,
A peeling test was performed using cellotape and evaluated according to the following criteria. ○ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling ×× ・ ・ Burning or peeling in the coating film

(Heat Resistance) A rosin-based plaque was applied to a test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as one cycle, and three cycles were repeated. After allowing to cool to room temperature, a peeling test was performed using cellophane tape, and evaluated according to the following criteria. 〇: No abnormality in the appearance of the coating film and no blistering or peeling ×: ...

(Gold Plating Resistance) A test substrate was subjected to 30 ° C. acidic degreasing solution (Metex L-5, manufactured by McDermit Japan).
B in a 20 vol% aqueous solution), washed with water, then immersed in a 14.4 wt% aqueous ammonium persulfate solution at room temperature for 3 minutes, washed with water, and further placed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute. After immersion for a minute, it was washed with water.
Next, this substrate was immersed in a 30 ° C. catalyst solution (manufactured by Meltex, a 10 vol% aqueous solution of a metal plate activator 350) for 7 minutes, washed with water, and washed at 85 ° C. with a nickel plating solution (manufactured by Meltex, Melplate Ni-). 865M 2
After immersing in a 0 vol% aqueous solution (pH 4.6) for 20 minutes and performing nickel plating, the substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute and washed with water. Next, the test substrate is
Immersion for 10 minutes in a gold plating solution (available from Meltex, 15 vol% of Aurolectroles UP and 3 vol% of gold potassium cyanide, pH 6), electroless gold plating, washing with water, and further heating with 60 ° C. warm water. Dipped for minutes, washed with water and dried. A cellophane adhesive tape was adhered to the obtained electroless gold-plated evaluation substrate, and the state when peeled off was observed. ：: No abnormality at all. X: Some peeling was observed.

Table 1 Example Comparative Example Note 1 1 2 1 2 Polycarboxylic acid resin containing unsaturated group (A) A-1-1 14.27 35.67 A-2-2 21.40 35.67 A-3-1 35.67 Crosslinking agent (B) DPHA * 1 6.82 6.82 6.82 6.82 Photopolymerization initiator (C) Irgacure 907 * 2 4.77 4.77 4.77 4.77 DETX-S * 3 0.48 0.48 0.48 0.48 Curing component (D) EOCN-104S * 4 8.18 8.18 EPPN-201 * 5 8.18 TEPIC-SP * 6 8.18 Hardening accelerator Melamine 1.02 1.02 1.02 1.02 Additive BYK-354 * 7 0.68 0.68 0.68 0.68 BYK-057 * 8 0.68 0.68 0.68 0.68 Filler Barium sulfate 20.45 20.45 20.45 20.45 Silica 7.50 7.50 7.50 7.50 Talc 0.68 0.68 0.68 0.68 Phthalocyanine green 0.55 0.55 0.55 0.55 Solvent carbitol acetate 12.52 12.52 12.52 12.52

Note * 1 Nippon Kayaku: dipentaerythritol hexaacrylate * 2 Ciba-Geigy: 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane * 3 Nippon Kayaku: 2, 4-Diethylthioxanthone * 4 Nippon Kayaku: o-cresol novolak type epoxy resin * 5 Nippon Kayaku: phenol novolak type epoxy resin 6 Nissan Chemical Industries: Tris (2,3-epoxypropyl) isocyanurate (poorly soluble) * 7 Made by Big Chemie: Leveling agent * 8 Made by Big Chemie: Antifoaming agent

Table 2 Example Comparative example 1 2 1 2 Evaluation item Developability ○ ○ ○ × Resolution ○ ○ × ○ Light sensitivity ○ ○ ○ ○ Surface gloss ○ ○ × ○ Substrate warpage ○ ○ ○ × Adhesion ○ ○ ○ ○ Pencil hardness 8H 8H 8H 8H Solvent resistance ○ ○ ○ ○ Acid resistance ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ Gold plating ○ ○ ○ ×

As is clear from the results in Table 2, the photosensitive resin composition of the present invention has high sensitivity and high resolution, can be developed with a dilute alkaline aqueous solution, and its cured film has a solder heat resistance. It is excellent in chemical resistance, gold plating resistance, etc., does not crack on the surface of the cured product, and does not warp the substrate even when using a thinned substrate. it is obvious.

[0068]

The photosensitive resin composition of the present invention can be applied to visible light, ultraviolet light, X-rays,
Excellent developability and photosensitivity when developing unexposed parts after irradiation with energy rays such as electron beams, and the resulting cured product has excellent adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating. It also satisfies the properties and the like, and is particularly suitable for a liquid solder resist ink composition for printed wiring boards.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 515 G03F 7/027 515 7/032 501 7/032 501 H05K 1/03 610 H05K 1/03 610L 3/28 3/28 DF term (for reference) 2H025 AA00 AA01 AA02 AA06 AA07 AA08 AB15 AC01 AC05 AC06 AD01 BC14 BC74 BC81 BC85 CC20 FA03 FA17 4J002 CD04X CD05X CD06X CD17W CD20W EE037 EE047 EU117E0EU E6767 EV317 EW147 FD14X FD146 FD157 GQ05 HA01 4J027 AC03 AE02 AE03 BA07 BA08 BA19 BA26 BA28 CA10 CC05 CD08 CD10 4J036 AA02 AA05 AD01 AD08 AF01 AF06 AF08 AF11 AK19 CA18 CA19 CA20 CD10 DA05 DA06 DB25 DC28 DC03 DC10 DC11 EA04 FB07 FB08 JA08 KA01 5E314 AA27 AA32 AA42 CC02 CC03 CC07 DD06 FF05 FF19 GG10 GG14 GG17 GG21

Claims (14)

[Claims] An unsaturated group-containing polycarboxylic acid resin (A),
Crosslinking agent (B), photopolymerization initiator (C) and curing component (D)
Wherein the unsaturated group-containing polycarboxylic acid resin (A) has two or more epoxy groups in the molecule and has an epoxy equivalent of 280 to 500 g / equivalent. -1) an unsaturated group-containing polycarboxylic acid resin (A-1) which is a reaction product of an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c), and Having two or more epoxy groups and an epoxy equivalent of 150 to 230 g / equivalent (a-
2) simultaneously containing an unsaturated group-containing polycarboxylic acid resin (A-2) which is a reaction product of an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c); A photosensitive resin composition comprising: 2. A reaction product of an epoxy resin (a-1) having two or more epoxy groups in a molecule and having an epoxy equivalent of 280 to 500 g / equivalent, and an unsaturated group-containing monocarboxylic acid (b). X is the solid weight of the unsaturated group-containing polycarboxylic acid resin (A-1), which is a reaction product between the polycarboxylic acid resin (A-1) and the polybasic acid anhydride (c), the epoxy resin having two or more epoxy groups in the molecule, and 150-230 g / equivalent epoxy resin (a-
When the solid content weight of the unsaturated group-containing polycarboxylic acid resin (A-2), which is a reaction product of 2) with an unsaturated group-containing monocarboxylic acid and a polybasic acid anhydride, is represented by Y, X The photosensitive resin composition according to claim 1, wherein the value of / Y is an unsaturated group-containing polycarboxylic acid resin (A) having a value of 0.25 or more and 4 or less. 3. An unsaturated group-containing polycarboxylic acid resin (A),
Crosslinking agent (B), photopolymerization initiator (C) and curing component (D)
Wherein the unsaturated group-containing polycarboxylic acid resin (A) has two or more epoxy groups in the molecule and has an epoxy equivalent of 280 to 500 g / equivalent. -1), and having two or more epoxy groups in the molecule, and having an epoxy equivalent of 150 to 230 g.
/ Unsaturated group which is a reaction product of an epoxy resin which is a mixture with an equivalent amount of epoxy resin (a-2), an unsaturated group-containing monocarboxylic acid (b), and a polybasic acid anhydride (c) A photosensitive resin composition, which is a polycarboxylic acid resin (A-3). 4. The epoxy resin (a-1) having two or more epoxy groups in the molecule and having an epoxy equivalent of 280 to 500 g / equivalent, the solid content weight is L, and two or more epoxy resins in the molecule. Having a group and an epoxy equivalent of 150 to 230 g
/ Equivalent weight of the solid content of the epoxy resin (a-2) as M, a mixture of an epoxy resin having an L / M value of 0.11 or more and 9 or less and an unsaturated group-containing monocarboxylic acid (b) 4. An unsaturated group-containing polycarboxylic acid resin (A-3), which is a reaction product of a polybasic acid anhydride (c) with a reaction product of (A-3).
3. The photosensitive resin composition according to item 1. 5. The epoxy resin (a-1) having two or more epoxy groups in the molecule and having an epoxy equivalent of 280 to 500 g / equivalent is a reaction product of a bisphenol type epoxy resin and epihalohydrin. Item 5. The photosensitive resin composition according to any one of Items 1 to 4. 6. An epoxy resin (a-2) having two or more epoxy groups in the molecule and having an epoxy equivalent of 150 to 230 g / equivalent is a novolak type epoxy resin or a polycondensation of phenol and hydroxybenzaldehyde. The photosensitive resin composition according to any one of claims 1 to 5, which is an epoxy resin. 7. An unsaturated group-containing monocarboxylic acid (b) comprising:
The photosensitive resin composition according to any one of claims 1 to 6, which is (meth) acrylic acid. 8. A polybasic acid anhydride (c) comprising: maleic anhydride;
The photosensitive resin composition according to any one of claims 1 to 7, which is a polybasic anhydride selected from succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. 9. The photosensitive resin composition according to claim 1, wherein the acid value of the solid content of the unsaturated group-containing polycarboxylic acid resin (A) is in the range of 50 to 150 mg · KOH / g. object. 10. The photosensitive resin composition according to claim 1, wherein the crosslinking agent (B) is a (meth) acrylate compound. 11. The photosensitive resin composition according to claim 1, wherein the curing component (D) is an epoxy resin soluble in an acetate solvent at room temperature. 12. The curing component (D) is an epoxy resin selected from a novolak type epoxy resin, a bisphenol type epoxy resin, an epoxy resin of a polycondensate of phenol and hydroxybenzaldehyde, and an epoxy resin having a naphthalene skeleton. The photosensitive resin composition according to any one of claims 1 to 11. 13. A cured product of the photosensitive resin composition according to any one of claims 1 to 12. 14. A printed circuit board having a layer of the cured product according to claim 13.