JP2003002958A - Polyester soluble in alkaline aqueous solution and photosensitive resin composition and cured product thereof using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent photosensitivity and providing a cured product having excellent flexibility, adhesion, pencil hardness and solvent, acid, heat and gold plating resistances. SOLUTION: A polyester (D) soluble in an alkaline solution is obtained by reacting a compound (A) with a compound (B) and a compound (C) as follows. The photosensitive resin composition and cured product is obtained from the polyester (D). The compound (A): an epoxy carboxylate compound obtained by reacting (a) an epoxy compound having two epoxy groups in a molecule with (b) a monocarboxylic acid having an ethylenically unsaturated double bond in a molecule. The compound (B): a diol compound having a spiro structure in the molecule. The compound (C): a polybasic acid anhydride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous alkaline solution-soluble polyester compound (D), a photosensitive resin composition using the same and a cured product thereof, and more specifically,
Useful as solder resist for flexible printed wiring board, plating resist, interlayer insulation film for multilayer printed wiring board, photosensitive optical waveguide, developability, electrical insulation, adhesion, solder heat resistance, chemical resistance, plating resistance The present invention relates to a resin composition that gives a cured product excellent in, and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Currently, solder resists for some consumer printed wiring boards and most industrial printed wiring boards are exposed to light and developed to form an image by heat treatment from the viewpoint of high accuracy and high density. Further, a liquid developing type solder resist which is finish-cured by light irradiation is used. Further, in consideration of environmental problems, an alkali developing type liquid solder resist using a dilute alkaline aqueous solution as a developing solution has become the mainstream. As an alkaline developing type solder resist using such a dilute aqueous alkaline solution, for example, in JP-A-61-243869, an acid anhydride is added to a reaction product of a novolac type epoxy resin and an unsaturated-basic acid. There is disclosed a solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy resin.

[0003]

A printed wiring board is a high-precision printed wiring board with the aim of reducing the size and weight of portable equipment and improving the communication speed.
Higher densities are required, and the demands on solder resists are becoming more and more sophisticated, and the performance that can withstand substrate adhesion, high insulation, and electroless gold plating is more flexible than conventional requirements. There is a demand, and the solder resists currently on the market cannot sufficiently meet these demands. The object of the present invention is to provide a fine image capable of accommodating the high-performance of today's printed wiring boards with excellent sensitivity to active energy rays, to form a pattern by development with a dilute aqueous alkaline solution, and to perform a post-curing step. It is an object of the present invention to provide a resin composition suitable for a solder resist ink having a cured film obtained by heat curing which has sufficient flexibility, high insulation properties, excellent adhesion, and excellent resistance to electroless gold plating, and a cured product thereof.

[0004]

The present inventors have completed the present invention as a result of earnest research on an aqueous alkaline solution-soluble polyester compound in order to solve the above-mentioned problems. That is, the present invention is

(1) Alkaline aqueous solution-soluble polyester compound (D), which is obtained by reacting compound (A), compound (B) and compound (C) shown below, compound (A): molecule An epoxycarboxylate compound compound (B) obtained by reacting an epoxy compound (a) having two epoxy groups in it with a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule: Diol compound compound (C) having a spiro structure in the molecule: polybasic acid anhydride (2) Epoxy compound having an epoxy equivalent of epoxy compound (a) having two epoxy groups in the molecule is 100 to 900 g / equivalent. The alkaline aqueous solution-soluble polyester compound (D) according to (1), and (3) the epoxy compound (a) having two epoxy groups in the molecule are Phenyl diglycidyl ether compound, bisphenol type epoxy compound, hydrogenated bisphenol type epoxy compound, halogenated bisphenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic diglycidyl ether compound, polysulfide type diglycidyl ether compound, biphenol type epoxy Compound or an epoxy compound selected from bixylenol type epoxy compounds (1) or (2), which is an aqueous alkaline solution-soluble polyester compound (D) according to any one of (2), and (4) ethylenic compounds in the molecule. The monocarboxylic acid compound (b) having a saturated double bond is a (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or a monocarboxylic acid selected from cinnamic acid ( 1) to (3) (5) The diol compound (compound (B)) having a spiro structure in the molecule is 3,9-bis (2-hydroxy-1,2).
1-Dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, wherein the aqueous alkaline solution-soluble polyester compound (D) according to any one of (1) to (4), 6) Polybasic acid anhydride (compound (C)) is pyromellitic anhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,3 , 4, -Butanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3',
4,4′-benzophenone tetracarboxylic acid dianhydride,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxy) Phenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2
-Dicarboxylic anhydride, from 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione The aqueous alkaline solution-soluble polyester compound (D) according to any one of (1) to (5), which is a selected polybasic acid anhydride, (7) having a solid content acid value of 50 to 150 mg · KOH / g. The alkaline aqueous solution-soluble polyester compound (D) according to any one of (1) to (6), and (8) the alkaline aqueous solution-soluble polyester compound according to any one of (1) to (7) D), a photopolymerization initiator (E), a cross-linking agent (F) and a curing component (G) as an optional component, a photosensitive resin composition, (9) The photosensitivity according to (8). Cured product of resin composition, ( 10) A substrate having a layer of the cured product according to (9), and (11) an article having the substrate according to (10).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous alkaline solution-soluble polyester compound (D) of the present invention is characterized by being obtained by reacting the above compound (A), compound (B) and compound (C).

The epoxy compound (a) having two or more epoxy groups in the molecule used for producing the aqueous alkaline solution-soluble polyester compound (D) of the present invention has an epoxy equivalent of 100 to 900 g / equivalent. The compound (a) is desirable. Epoxy equivalent is 10
If it is less than 0, the resulting aqueous alkaline solution-soluble polyester compound (D) may have a small molecular weight, which may make it difficult to form a film, or may not provide sufficient flexibility.
On the other hand, when the epoxy equivalent exceeds 900, the introduction rate of the monocarboxylic acid (b) having an ethylenically unsaturated double bond may be low and the photosensitivity may be lowered.

Specific examples of the epoxy compound having two epoxy groups in the molecule include, for example, phenyldiglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol-A type epoxy resin. , Bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, bisphenol type epoxy such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound Compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3 , 3,
Hydrogenated bisphenol type epoxy compounds such as 3-hexafluoropropane epoxy compounds, brominated bisphenol-A type epoxy resins, halogenated bisphenol type epoxy compounds such as brominated bisphenol-F type epoxy resins, cyclohexanedimethanol diglycidyl ether compounds Alicyclic diglycidyl ether compounds such as
1,6-hexanediol diglycidyl ether, 1,
Examples thereof include aliphatic diglycidyl ether compounds such as 4-butanediol diglycidyl ether and diethylene glycol diglycidyl ether, polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether, and biphenol type epoxy resin.

Commercially available products of these epoxy compounds are:
For example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 100
4 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-3
04 (all manufactured by Mitsui Chemicals), DER-331, DER
-332, DER-324 (all manufactured by Dow Chemical Co.), Epicron 840, Epiclon 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide Co.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), etc. Bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide Co.), YDF-2001, YDF-2
004, YDF-8170 (all manufactured by Tohto Kasei Co., Ltd.),
Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (all manufactured by Dainippon Ink and Chemicals), H
BPA-DGE (Maruzen Petrochemical Co., Ltd.), Lycaredin HBE
− Hydrogenated bisphenols such as 100 (manufactured by Shin Nippon Rika) −
A type epoxy resin, DER-513, DER-514,
Brominated bisphenol-A type epoxy resin such as DER-542 (all manufactured by Dow Chemical Co., Ltd.), Celoxide 2021 (manufactured by Daicel), Rikaresin DME-100
(Nippon Rika), EX-216 (Nagase Kasei) and other alicyclic epoxy resins, ED-503 (Asahi Denka), Licarezin W-100 (Nippon Rika), EX-212, E
X-214, EX-850 (both manufactured by Nagase Kasei), etc., aliphatic diglycidyl ether compound, FLEP-5
0, FLEP-60 (all manufactured by Toraythiocol), polysulfide-type diglycidyl ether compound, YX
Biphenol-type epoxy compounds such as -4000 (manufactured by Japan Epoxy Resin).

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule used for producing the aqueous alkaline solution-soluble polyester compound (D) of the present invention include acrylic acids, crotonic acid, α
-Cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydrides, and (meth) acrylate derivatives having one hydroxyl group in one molecule. And a half-ester which is an equimolar reaction product, and a half-ester which is an equimolar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative. In terms of sensitivity when (meta)
Acrylic acid, the reaction product of (meth) acrylic acid and ε-caprolactone or cinnamic acid is particularly preferred.

The diol compound (B) having a spiro structure in the molecule used for producing the aqueous alkaline solution-soluble polyester compound (D) of the present invention is an organic compound having two rings and one Any compound having a structure in which atoms are shared by two rings and having two alcoholic hydroxyl groups in the molecule can be used. Specific examples of these structures include, for example, spiro [2.2] pentane structure, spiro [3.3] heptane structure, spiro [2.4] heptane structure, spiro [2.5]
Octane structure, spiro [3.4] octane structure, spiro [4.4] nonane structure, spiro [3.5] nonane structure,
Examples thereof include spiro [2.6] nonane structure, spiro [4.5] decane structure, spiro [5.5] undecane structure and the like. Further, not only carbon atoms but also hetero atoms may be present in the ring structure, and in particular, 3,9-bis (2
-Hydroxy-1,1-dimethylethyl) -2,4
8,10-Tetraoxaspiro [5.5] undecane is preferred.

The polybasic acid anhydride (compound (C)) used for producing the aqueous alkaline solution-soluble polyester compound (D) of the present invention may be one having at least two acid anhydride structures in the molecule. All can be used, but pyromellitic dianhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,
3,4, -butanetetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid 2 Anhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-an) Hydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4
5,9b-tetrahydro-5- (tetrahydro-2,5
Particularly preferred is a polybasic acid anhydride selected from -dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione.

The production of the aqueous alkaline solution-soluble polyester compound (D) of the present invention is carried out by the above-mentioned epoxy compound (a).
With a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule (hereinafter referred to as the first reaction)
To obtain an epoxycarboxylate compound (A) in which an alcoholic hydroxyl group is formed, and then to obtain the epoxycarboxylate compound (A) and the diol compound (B) having a spiro structure in the molecule, a polybasic acid anhydride (C). )
The esterification reaction (hereinafter referred to as the second reaction) can be carried out.

The first reaction is solvent-free or a solvent having no alcoholic hydroxyl group, specifically, acetone, ethyl methyl ketone, ketones such as cyclohexanone, benzene, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve Acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glue Esters such as dialkyl acid salts, dialkyl succinates, and dialkyl adipates, cyclic esters such as γ-butyrolactone, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, and the crosslinking agent described later. It can be carried out in a single or mixed organic solvent such as (F).

The ratio of the raw materials charged in this reaction is 80 to 80 for 1 equivalent of the epoxy compound (a) for the monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. It is preferably 120 equivalent%. If it deviates from this range, it may cause gelation during the second reaction, or the thermal stability of the finally obtained alkaline aqueous solution-soluble polyester compound (D) may be lowered, which is not preferable.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is usually 0.1 to 10% by weight based on the reactant. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine,
Triphenylstibine, methyltriphenylstibine,
Examples thereof include chromium octanoate and zirconium octanoate.

In the second reaction, after the completion of the first reaction, the diol compound (B) having a spiro structure in the molecule is added to the reaction solution to form a dispersion or solution, and then the above-mentioned polybasic acid is added. It is an esterification reaction in which an anhydride (C) is gradually added and reacted. Although the reaction can be carried out without a catalyst, the basic catalyst as described above can be used to accelerate the reaction, and the amount of the catalyst used is 10% by weight or less based on the reactant. The reaction temperature at this time is 4
0 to 120 ° C., and the reaction time is preferably 5 to
60 hours. Further, the epoxycarboxylate compound (A) obtained in the first reaction may be isolated and then used in the second reaction.

In the charged amounts of the respective components, the calculated solid content acid value of the aqueous alkaline solution-soluble polyester compound (D) of the present invention as the polybasic acid anhydride (C) is 50 to 1.
Use an amount of 50 mg · KOH / g, and make the ratio of (the number of moles of compound (A) + the number of moles of compound (B)) / (the number of moles of compound C) be in the range of 1 to 5. It is preferable to charge it in. When this value is less than 1, an acid anhydride group will remain at the terminal of the aqueous alkaline solution-soluble polyester compound (D) of the present invention, and the thermal stability is low and gelation may occur during storage, which is preferable. Absent. On the other hand, when this value exceeds 5, the molecular weight of the aqueous alkaline solution-soluble polyester compound (D) becomes low, which may cause problems of tackiness and low sensitivity. Further, when the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, it may remain as a residue or, in the worst case, patterning may not be possible. The solid acid value is 150
When it exceeds mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high and the photocured pattern may peel off, which is not preferable.

The photosensitive resin composition of the present invention contains the above-mentioned aqueous alkaline solution-soluble polyester compound (D), a photopolymerization initiator (E), a cross-linking agent (F), and a curing component (G) as an optional component. Is characterized by.

The content ratio of the above-mentioned aqueous alkaline solution-soluble polyester compound (D) used in the photosensitive resin composition of the present invention is 100% based on the solid content of the photosensitive resin composition.
When it is defined as weight%, it is usually 15 to 70 weight%, preferably 20 to 60 weight%.

Specific examples of the photopolymerization initiator (E) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxy-2-phenylacetophenone, 2,2-
Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Acetophenones such as morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-
Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,
Benzophenones such as 4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the addition ratio of these, the solid content of the photosensitive resin composition is 100% by weight.
, 1 to 30% by weight, preferably 2 to 2
It is 5% by weight.

These can be used alone or as a mixture of two or more kinds, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid. It can be used in combination with a promoter such as a benzoic acid derivative such as acid isoamyl ester.
The amount of these accelerators added is such that the photopolymerization initiator (E)
On the other hand, the addition amount of 100% or less is preferable.

Specific examples of the crosslinking agent (F) used in the photosensitive resin composition of the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 1,4-butane. Diol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol) A half ester which is a reaction product of an acid anhydride (for example, succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) of a poly (carboxylic acid) compound with mono (meth) acrylate, etc. Polyethylene glycol di (meth) acrylate, Lipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, hydroxypivalate neopen glycol addition of ε-caprolactone Di (meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAY
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl. Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Epoxy (meth) which is a reaction product of (meth) acrylic acid An acrylate etc. can be mentioned. The addition ratio of these is usually 2 to 40% by weight, preferably 5 to 30% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

Examples of the curing component (G) as an optional component used in the photosensitive resin composition of the present invention include epoxy compounds and oxazine compounds. Curing component (G)
Is particularly preferably used in the case of reacting with a carboxyl group remaining in the resin coating film after photocuring by heating to obtain a cured coating film having stronger chemical resistance.

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

Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc.), D.I. E. N438 (manufactured by Dow Chemical Co.), Epicoat 154 (Yukaka Shell Epoxy Co., Ltd.)
Manufactured by Nippon Kayaku Co., Ltd., and the like. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (made by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503 and EPPN-
502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Co.), Epicoat E1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Etc. Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-720.
0 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-
556 (manufactured by Dow Chemical Co.) and the like.

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (made by Yuka Shell Epoxy), UVR-6410 (made by Union Carbide), D.I. E. R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.) and other bisphenol-A type epoxy resins, UVR-6490 (manufactured by Union Carbide Co.), YDF-8170 (manufactured by Toto Kasei Co., Ltd.)
And other bisphenol-F type epoxy resins.

As the biphenol type epoxy resin, for example, biphenol type epoxy resins such as NC-3000P, NC-3000S (Nippon Kayaku Co., Ltd.), YX-4.
000 (produced by Yuka Shell Epoxy Co., Ltd.) and bixylenol type epoxy resin, YL-6121 (produced by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolac type epoxy resin include Epiclon N-8.
80 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat E
157S75 (produced by Yuka Shell Epoxy Co., Ltd.) and the like.

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.) and the like. Examples of the alicyclic epoxy resin include EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.) and the like. Examples of the heterocyclic epoxy resin include TEPl
C, TEPIC-L, TEPIC-H, TEPIC-S
(Both manufactured by Nissan Chemical Industries, Ltd.) and the like.

Specific examples of the oxazine compound used as the curing component (G) include, for example, Bm type benzoxazine, Pa type benzoxazine, and Ba type benzoxazine (all manufactured by Shikoku Chemicals Co., Ltd.). Is mentioned.

As the addition ratio of the curing component (G), an equivalent amount of 200 calculated from the acid value of the solid content of the alkali aqueous solution-soluble epoxycarboxylate compound of the present invention and the amount used.
% Or less is preferred. If this amount exceeds 200%, the developability of the photosensitive resin composition of the present invention may be significantly reduced, which is not preferable.

The curing component (G) may be mixed with the resin composition in advance, but may be mixed before being applied to the printed wiring board. That is, the above
The main component solution mainly composed of the component (A), which is mixed with an epoxy curing accelerator and the like, and the main component solution mainly composed of the component (D) are mixed into a two-part type, and these are mixed and used at the time of use. It is preferable.

Further, if necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and other fillers, and thixotropy such as aerosil. Agents; phthalocyanine blue, phthalocyanine green, colorants such as titanium oxide, silicone, fluorine-based leveling agents and defoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are added for the purpose of enhancing various properties of the composition. You can

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

The photosensitive resin composition (liquid or film form) of the present invention is used as an insulating material between layers of electronic parts, a solder resist for optical waveguides or printed boards for connecting optical parts, a resist material for a coverlay, etc. Besides being useful, it can also be used as a color filter, a printing ink, a sealant, a paint, a coating agent, an adhesive, and the like.

The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing can be carried out by an ordinary method by irradiation with energy rays such as ultraviolet rays. For example, when irradiating with ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (excimer laser, etc.) may be used.

The cured product of the resin composition of the present invention is used, for example, as a resist film, an interlayer insulating material for a build-up construction method, and an optical waveguide for electric / electronic / optical parts such as a printed circuit board, an optoelectronic board and an optical board. It Specific examples of these include computers, home appliances, mobile devices, and the like. The thickness of this cured product layer is usually 0.5 to 160.
About μm, preferably about 1 to 100 μm.

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention can be applied to a printed wiring board by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc., in a film thickness of 5 to 160 μm. By applying the composition of (1) and drying the coating film at a temperature of usually 50 to 110 ° C, preferably 60 to 100 ° C,
A coating film can be formed. After that, a high energy ray such as ultraviolet ray is usually applied to the coating film directly or indirectly through a photomask on which an exposure pattern such as a negative film is formed in an amount of 10 to 2000.
Irradiation with an intensity of about mJ / cm ^{2 is performed} , and the unexposed portion is developed by using a developer described later, for example, by spraying, rocking dipping, brushing, scrubbing and the like. Then, if necessary, further irradiate with ultraviolet rays, and then usually 100-
By performing heat treatment at a temperature of 200 ° C., preferably 140 to 180 ° C., a permanent protective film having excellent gold plating properties and satisfying various properties such as heat resistance, solvent resistance, acid resistance, adhesion and flexibility is obtained. A printed wiring board having the same can be obtained.

Examples of the alkaline aqueous solution used for the development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate and potassium phosphate. Organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and the like can be used. The pH of the alkaline aqueous solution is usually 8 or more, preferably 9
Prepare to be ~ 12.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1 In a 2 L flask equipped with a stirrer and a reflux tube, RE-310S (bifunctional bisphenol-A manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound (a) having two or more epoxy groups in the molecule. Type epoxy resin, epoxy equivalent: 182.2g
/ Equivalent), 364.4 g, 144.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule, and 2-methyl as a thermal polymerization inhibitor. 0.24 g of hydroquinone,
And triphenylphosphine as a reaction catalyst 1.4
Charged 5 g, the acid value of the reaction solution was 0.5 mg at a temperature of 98 ° C.
-The reaction was continued until it became KOH / g or less to obtain an epoxycarboxylate compound (A) (theoretical molecular weight: 508.5). Next, 555.2 g of carbitol acetate as a solvent for reaction was added to this reaction solution, and SPG (3,9-bis (2-hydroxy-) was used as a diol compound (B) having a spiro structure in the molecule.
1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane) (molecular weight: 30)
4.38) and 30.40 g of 2-methylhydroquinone as a thermal polymerization inhibitor were added, and the temperature was raised to 80 ° C. To this solution, 218.1 g of PMDA (pyromellitic anhydride (molecular weight: 218.1)) manufactured by MC DuPont was added as a polybasic acid anhydride (C). After the addition, the temperature is raised to 95 ° C. and the reaction is allowed to proceed for 6 hours.
To obtain a resin solution (this solution is referred to as D-1). When the acid value was measured, it was 66.9 mg · KOH / g (solid content acid value: 102.9 mg · KOH / g).

Example 2 In a 2 L flask equipped with a stirrer and a reflux tube, as an epoxy compound (a) having two or more epoxy groups in the molecule, YX-4000 (2 manufactured by Japan Epoxy Resin)
Functional bixylenol type epoxy resin, epoxy equivalent: 1
(96.0 g / equivalent) 392.0 g, a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule
Acrylic acid (molecular weight: 72.06) as 144.1
g, 0.27 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.61 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution at a temperature of 98 ° C. was 0.5 mg · KOH / g or less. Until the epoxy carboxylate compound (A) (theoretical molecular weight: 5
36.1) was obtained. Next, 645.5 g of carbitol acetate as a reaction solvent was added to this reaction solution, and SPG (3,9-bis (2) (2) produced by Japan Hydrazine Industry Co., Ltd. was used as a diol compound (B) having a spiro structure in the molecule.
-Hydroxy-1,1-dimethylethyl) -2,4
8,10-Tetraoxaspiro [5.5] undecane)
(Molecular weight: 304.38) 304.4 g, 2-methylhydroquinone 0.92 g as a thermal polymerization inhibitor,
The temperature was raised to 80 ° C. Add polybasic acid anhydride (C) to this solution
As a new Nippon Rika DSDA (3,3 ', 4,4'
358.3 g of diphenylsulfone tetracarboxylic acid dianhydride: molecular weight 358.28) was added. After the addition, the temperature was raised to 95 ° C. and the reaction was carried out for 8 hours to obtain a resin solution containing 65% by weight of the aqueous alkaline solution-soluble polyester compound of the present invention (this solution is referred to as D-2). When the acid value was measured, it was 61.8 mg · KOH / g (solid content acid value: 95.1 mg · KOH / g).

Example 3 In a 2 L flask equipped with a stirrer and a reflux tube, as an epoxy compound (a) having two or more epoxy groups in the molecule, YX-8000 (2 manufactured by Japan Epoxy Resin) was used.
404.1 g of functional hydrogenated bisphenol-A type epoxy resin, epoxy equivalent: 202.06 g / equivalent, acrylic acid (molecular weight: 72) as the monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. .06)
144.1 g, hydroquinone monomethyl ether as a thermal polymerization inhibitor 1.10 g, and triphenylphosphine as a reaction catalyst 1.61 g were charged, and the acid value of the reaction solution at a temperature of 98 ° C. was 0.5 mg · KOH / g. The reaction was carried out until the following conditions were obtained to obtain an epoxycarboxylate compound (A) (theoretical molecular weight: 548.2). Then, methyl ethyl ketone was added to the reaction solution as a reaction solvent.
6.5 g, SPG manufactured by Japan Hydrazine Industry Co., Ltd. as a diol compound (B) having a spiro structure in the molecule
(3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.
5] Undecane) (molecular weight: 304.38).
4 g and 3.29 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added, and the temperature was raised to 80 ° C. As a polybasic acid anhydride (C), PMDA (pyromellitic anhydride (molecular weight: 21
8.1)) 218.1 g were added. After the addition, increase the temperature to 9
The temperature was raised to 5 ° C., and the reaction was performed for 6 hours to obtain a resin solution containing 65% by weight of the aqueous alkaline solution-soluble polyester compound of the present invention (this solution is referred to as D-3). When the acid value was measured, it was 70.0 mg · KOH / g (solid content acid value: 10
It was 7.7 mgKOH / g).

Examples 4 and 5 (D-1) and (D-2) obtained in the above-mentioned Examples 1 and 2 were mixed in a mixing ratio shown in Table 1, and if necessary, kneaded by a three-roll mill. Then, the photosensitive resin composition of the present invention was obtained. This was screen-printed to give a dry film thickness of 15
It was applied to a printed circuit board so as to have a thickness of ˜25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Then
UV exposure system (Oak Co., Ltd., model HMW-6)
Ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using 80 GW). After that, spray development was performed with a 1% sodium carbonate aqueous solution to remove the resin in the portion not irradiated with ultraviolet rays. After washing with water and drying, the printed board was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film. The obtained cured product, as described below, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness, solvent resistance,
The acid resistance, heat resistance, and gold plating resistance were tested. The results are shown in Table 2. The test method and evaluation method are as follows.

(Tackiness) The dried film applied to the substrate was rubbed with absorbent cotton to evaluate the tackiness of the film. ○ ・ ・ ・ ・ The absorbent cotton does not stick. × ・ ・ ・ ・ The cotton lint sticks to the film.

(Developability) The following evaluation criteria were used. ○ ... ・ Ink was completely removed during development and development was possible. X ...- Some areas are not developed during development.

(Resolution) A 50 μm negative pattern is brought into close contact with the dried coating film and exposed to ultraviolet rays with an integrated light amount of 200 mJ / cm ² . Next, it is developed with a 1% sodium carbonate aqueous 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 jagged pattern edges.

(Photosensitivity) 21 steps of step tablets (manufactured by Kodak Co., Ltd.) are brought into close contact with the coating film after drying and the integrated light amount is 50.
It is exposed to ultraviolet light of 0 mJ / cm ² . Next, it is developed with a 1% sodium carbonate aqueous solution 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.

(Surface gloss) 500 mJ on the coating film after drying
Irradiate and expose with ultraviolet rays of / cm ² . Then, it is developed with a 1% sodium carbonate aqueous solution 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 cloudiness is observed × ・ ・ ・ ・ Slight cloudiness is observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ ・ No warpage on the substrate △ ・ ・ ・ ・ Slightly warped substrate × ・ ・ ・ ・ Warp of the substrate can be seen

(Flexibility) The cured film is bent at 180 ° C. and observed. The following criteria were used. ○ ・ ・ ・ ・ No cracks are seen on the film surface × ・ ・ ・ ・ The film surface is cracked

(Adhesion) According to JIS K5400,
100 1 mm squares were made on the test piece, and a peeling test was performed using Cellotape (R). The peeling state of the first eye was observed and evaluated according to the following criteria. ○ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ Peeling

(Pencil Hardness) The pencil hardness was evaluated according to JIS K5400.

(Solvent resistance) The test piece is immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there is no abnormality in the appearance, a peeling test using Cellotape (R) was performed and evaluated according to the following criteria. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Acid resistance) The test piece is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there is no abnormal appearance,
A peeling test using Cellotape (R) was performed and evaluated according to the following criteria. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Heat Resistance) A rosin-based plaque was applied to the test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was set as one cycle and repeated for three cycles. After allowing to cool to room temperature, a peeling test using Cellotape (R) was performed and evaluated according to the following criteria. 〇 ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Gold Plating Resistance) A test substrate was treated with an acidic degreasing solution (Metex L-5, manufactured by Nippon McDermitt) at 30 ° C.
(20 vol% aqueous solution of B) for 3 minutes, then washed with water, then immersed in 14.4 wt% ammonium persulfate aqueous solution for 3 minutes at room temperature, and then washed with water, and further test substrate was immersed in 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute. After dipping for a minute, it was washed with water.
Next, this substrate was immersed in a catalyst solution at 30 ° C (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and a nickel plating solution at 85 ° C (Meltex Ni-Melplate Ni- 2 of 865M
It was dipped in a 0 vol% aqueous solution, pH 4.6) for 20 minutes to perform nickel plating, and then dipped in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Then, the test board is
Immersing in a gold plating solution at ℃ (Meltex, an aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium gold cyanide, pH 6) for 10 minutes to perform electroless gold plating, followed by rinsing with water and further heating with hot water at 60 ° C. It was soaked for a minute, washed with water and dried. A cellophane adhesive tape was attached to the obtained electroless gold-plated evaluation substrate, and the state of peeling was observed. ◯: No abnormality. X: Some peeling was observed.

(PCT resistance) After the test substrate was left in water at 121 ° C. and 2 atm for 96 hours, it was confirmed that there was no abnormality in appearance, and then a peeling test was performed using Cellotape (R).
The following criteria evaluated. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Thermal shock resistance) The test piece was tested at -55 ° C / 30.
Min, 125 ° C./30 minutes as one cycle, a thermal history is added, and after 1000 cycles, the test piece is observed under a microscope.
The following criteria evaluated. ○ ・ ・ ・ ・ No cracks in the coating film × ・ ・ ・ ・ ・ ・ Cracks in the coating film

[0061] Table 1                                       Example Note 45 Resin solution   D-1 51.80   D-2 51.80 Cross-linking agent (F)   DPCA * 1 3.38   HX-220 * 2 3.38 Photopolymerization initiator (E)   Irgacure 907 * 3 4.50 4.50   DETX-S * 4 0.45 0.45 Curing component (G)   YX-4000 * 5 17.62 17.62 Thermosetting catalyst   Melamine 1.00 1.00 Filler   Barium sulfate 15.15 15.15   Phthalocyanine blue 0.45 0.45 Additive   BYK-354 * 6 0.39 0.39   KS-66 * 7 0.39 0.39 solvent CA 4.87 4.87

Note * 1 Nippon Kayaku: ε-caprolactone modified dipentaerythritol hexaacrylate * 2 Nippon Kayaku: ε-caprolactone modified hydroxypivalic acid neopentyl glycol diacrylate * 3 Vantico: 2-methyl- (4 -(Methylthio) phenyl) -2-morpholino-1-propane * 4 Nippon Kayaku: 2,4-diethylthioxanthone * 5 JER: Bifunctional bixylenol type epoxy resin * 6 BYK Chemie: Leveling agent * 7 Shin-Etsu Chemical Made by: Antifoam

Table 2 Example 45 Evaluation item Tackiness ○ ○ Developability ○ ○ Resolution ○ ○ Light sensitivity 12 11 Surface gloss ○ ○ Substrate sled ○ △ Flexibility ○ ○ Adhesion ○ ○ Pencil hardness 6H 7H Solvent resistance ○ ○ Acid resistance ○ ○ Heat resistance ○ ○ Gold plating resistance ○ ○ PCT resistance ○ ○ Thermal shock resistance ○ ○

Example 6 54.44 g of the resin solution (D-3) obtained in Example 3,
As a cross-linking agent (F), 3.54 g of HX-220 (trade name: bifunctional acrylate resin manufactured by Nippon Kayaku), and as a photopolymerization initiator (E), Irgacure 907 (trade name: photopolymerization initiator manufactured by Bantico) 4.72g and Kayacure D
ETX-S (trade name: photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.) was used.
47 g, YX-8000 as a curing component (G) (trade name: Japan epoxy resin, bifunctional hydrogenated bisphenol-A type epoxy resin, epoxy equivalent: 202.06)
g / equivalent) of 14.83 g, melamine of 1.05 g as a thermosetting catalyst and methyl ethyl ketone of 20.95 g as a concentration-adjusting solvent were added, and the mixture was kneaded and uniformly dispersed in a bead mill to obtain a photosensitive resin composition of the present invention. .

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

Next, ultraviolet rays were irradiated (irradiation dose: 500 mJ / square centimeter) using an ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern. After irradiation, the support film was peeled off from the resin,
It was developed with a 5% tetramethylammonium aqueous solution for 30 seconds to dissolve and remove the unirradiated portion. After washing with water and drying, the printed board was subjected to a heat curing reaction for 30 minutes in a hot air dryer at 150 ° C. to obtain a cured film. The resulting cured product has good transparency and is 5
A 0 μm pattern was resolved.

As is apparent from the above results, the alkaline aqueous solution-soluble polyester compound of the present invention and the photosensitive resin composition using the same have no tackiness and high sensitivity, and the cured film thereof has solder heat resistance, It is clear that it is a photosensitive resin composition for printed circuit boards that has excellent chemical resistance, resistance to gold plating, etc., does not cause cracks on the surface of the cured product, and has less warpage even when using a thin film substrate. Is.

[0068]

EFFECT OF THE INVENTION An aqueous alkaline solution-soluble polyester compound, a photosensitive resin composition using the same, and a cured product thereof have excellent photosensitivity in the formation of a coating film by exposure and curing with ultraviolet light, and the resulting cured product is , Flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, etc. are also sufficiently satisfied, and in particular, a photosensitive resin composition for printed wiring boards and a photosensitive material for forming an optical waveguide. Suitable for a resin composition.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA04 AA14 AB15 AB20 AC01                       AD01 BC03 BC13 BC42 BC63                       BC82 BC85 BJ10 CA00 CC17                       FA17                 4J029 AA07 AB01 AD02 AD10 AE18                       BD10 FC35 FC36 GA42 GA51                       HB06                 5E314 AA27 AA32 CC07 DD07 FF06                       GG08 GG14                 5E343 AA33 CC63 ER12 ER16 ER18                       GG16                 5E346 AA12 CC09 DD02 DD03 HH18

Claims (11)

[Claims] 1. An alkaline aqueous solution-soluble polyester compound (D) obtained by reacting the following compound (A), compound (B) and compound (C). Compound (A): Epoxycarboxylate obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule Compound compound (B): diol compound having a spiro structure in the molecule Compound (C): polybasic acid anhydride. 2. The epoxy equivalent of the epoxy compound (a) having two epoxy groups in the molecule is 100 to 900 g /.
The aqueous alkaline solution-soluble polyester compound (D) according to claim 1, which is an equivalent amount of an epoxy compound. 3. An epoxy compound (a) having two epoxy groups in the molecule is a phenyl diglycidyl ether compound, a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, a halogenated bisphenol type epoxy compound, an alicyclic group. Diglycidyl ether compound,
The alkali according to any one of claims 1 and 2, which is an epoxy compound selected from an aliphatic diglycidyl ether compound, a polysulfide-type diglycidyl ether compound, a biphenol-type epoxy compound, and a bixylenol-type epoxy compound. Aqueous solution-soluble polyester compound (D). 4. A monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule is a (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone or cinnamic acid. The alkali aqueous solution-soluble polyester compound (D) according to any one of claims 1 to 3, which is a monocarboxylic acid selected from the above. 5. A diol compound having a spiro structure in the molecule (compound (B)) is 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxa. The alkaline aqueous solution-soluble polyester compound (D) according to any one of claims 1 to 4, which is spiro [5.5] undecane. 6. A polybasic acid anhydride (compound (C)) is pyromellitic dianhydride, ethylene glycol-bis (anhydrotrimellitate), glycerin-bis (anhydrotrimellitate) monoacetate, 1, 2,3,4, -Butanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-
Diphenyl sulfone tetracarboxylic acid dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro) -3-furanyl) -3-methylcyclohexene-1,
2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-
Furanyl) -naphtho [1,2-c] furan-1,3-dione is a polybasic acid anhydride selected from the group consisting of:
An alkaline aqueous solution-soluble polyester compound (D) according to any one of claims 1 to 5. 7. The acid value of solid content is 50 to 150 mg.KOH
/ G, and the aqueous alkaline solution-soluble polyester compound (D) according to any one of claims 1 to 6. 8. An alkaline aqueous solution-soluble polyester compound (D) according to any one of claims 1 to 7, a photopolymerization initiator (E), a crosslinking agent (F) and a curing component (G) as an optional component. ) Is contained, The photosensitive resin composition characterized by the above-mentioned. 9. A cured product of the photosensitive resin composition according to claim 8. 10. A substrate having a layer of the cured product according to claim 9. 11. An article having the substrate according to claim 10.