JP2003122001A - Photosensitive resin, photosensitive resin composition using the same, and its hardened product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in photosensitivity and of which hardened product is excellent in bending property, adhesion property, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance or the like. SOLUTION: The photosensitive resin composition contains a polyester urethane compound (E) soluble with an alkali aqueous solution obtained by the reaction of the following compound (A), compound (B) and compound (D), and as an optional component, compound (C). The compounds are (A) an epoxy carboxylate compound obtained by the reaction of an epoxy compound (a) having two epoxy groups in the molecule and a monocarboxylic acid compound having an ethylenic unsaturated group in the molecule, (B) a diisocyanate compound, (C) a diol compound except for the compound (A), and (D) 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 an aqueous alkaline solution-soluble polyester urethane compound (E), a photosensitive resin composition using the same, and a cured product thereof, and more specifically, a solder resist for flexible printed wiring boards and a plating resist. , A resin composition giving a cured product which is useful as an interlayer insulating film for a multilayer printed wiring board, a photosensitive optical waveguide, etc. and which has excellent developability, electrical insulation, adhesion, solder heat resistance, chemical resistance, plating resistance, etc. 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. However, this composition is rigid and has no flexibility. Then, the patent publication 2001-1
No. 63948 proposes a method for producing a photoimageable composition containing a flexible oligomer, which comprises reacting a polyfunctional epoxy compound with an ethylenically unsaturated oligomer and then with a diisocyanate compound.

[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 urethane compound in order to solve the above-mentioned problems. That is, the present invention is

(1) Alkaline aqueous solution soluble polyester urethane compound characterized by being obtained by reacting the following compound (A), compound (B), compound (D), and optionally compound (C) (E). Compound (A): Epoxycarboxylate compound compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (B): diisocyanate compound compound (C): diol compound other than compound (A) compound (D): polybasic acid anhydride. (2) Epoxycarboxylate compound (A) obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule And a diisocyanate compound (B) and, optionally, a diol compound (C), and then reacting the polybasic acid anhydride (D) with the aqueous alkaline solution-soluble polyester urethane compound according to (1). (E) manufacturing method,
(3) Epoxycarboxylate compound (A) obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule X equivalent to the charged equivalent of
The production method of an aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of (1) and (2), wherein the equivalent ratio is x> y when the charged equivalent of the diisocyanate compound (B) is y equivalent. , (4) Epoxycarboxylate compound (A obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (A) ) And a polybasic acid anhydride (D),
A method for producing an alkaline aqueous solution-soluble polyester urethane compound (E) according to (1), which comprises reacting a diisocyanate compound (B), (5) an epoxy compound (a) having two epoxy groups in the molecule. And the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule are reacted to obtain an epoxycarboxylate compound (A) in the amount of x'equivalent, polybasic acid anhydride (D) in the same amount. When the equivalent is defined as y'equivalent, the equivalent ratio is x '>y', (1) or (4), the method for producing an alkaline aqueous solution-soluble polyester urethane compound (E), (6) After the reaction between the diisocyanate compound (B) and the diol compound (C), 2 in the molecule
Epoxy carboxylate compound (A) obtained by reacting an epoxy compound (a) having one epoxy group with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and a polybasic acid anhydride ( (7), wherein the alkali aqueous solution-soluble polyesterurethane compound (E) is reacted with D).
When the charged equivalent of the diisocyanate compound (B) is x "equivalent and the charged equivalent of the diol compound (C) is y" equivalent, the equivalent ratio is x "<y", either (1) or (6). Item 8. A method for producing an aqueous alkaline solution-soluble polyester urethane compound (E) according to the item, (8) 2 in the molecule
The epoxy aqueous solution-soluble polyester urethane compound (E) according to any one of (1) to (7), wherein the epoxy compound having one epoxy group (a) has an epoxy equivalent of 100 to 900 g / equivalent. ,
(9) The 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 diglycidyl compound. An epoxy compound selected from an ether compound, an aliphatic diglycidyl ether compound, a polysulfide type diglycidyl ether compound, a biphenol type epoxy compound or a bixylenol type epoxy compound (1) to (8) The monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule of the aqueous alkaline solution-soluble polyester urethane compound (E) and (10) described above is (meth).
The aqueous alkaline solution-soluble polyester according to any one of (1) to (9), which is a monocarboxylic acid selected from acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid. Urethane compound (E), (11) diisocyanate compound (B) is phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate , Isophorone diisocyanate, allylene sulfone ether diisocyanate, allyl cyan diisocyanate, N-acyl diisocyanate, trimethyl Hydroxyl group of the alkaline aqueous solution-soluble polyester urethane compound (E) and (12) diol compound (C) according to any one of (1) to (10), which is a compound selected from hexamethylene diisocyanate or lysine diisocyanate. Wherein (13) a polybasic acid anhydride (D) is a photosensitive resin containing the aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of (1) to (11), wherein is an alcoholic hydroxyl group. 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 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 acid anhydride, 3a, 4
5,9b-tetrahydro-5- (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, which is a polybasic acid anhydride selected from (1) to (12). Alkali aqueous solution soluble polyester urethane compound (E), (14) solid content acid value is 30 to 150 mg · K
OH / g, the aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of (1) to (13), and the alkaline aqueous solution according to any one of (15), (1) to (14). Photosensitive resin composition containing soluble polyester compound (E), (16) (15)
The photosensitive resin composition according to (1), which contains a photopolymerization initiator (F), a crosslinking agent (G) and a curing component (H) as an optional component, (17) ( 1
5) or a cured product of the photosensitive resin composition according to any one of (16), a substrate having a layer of the cured product according to (18) or (17), or (19) or (18) To provide an article having the substrate.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention comprises an epoxy compound (a) having two epoxy groups in the molecule and a monocarboxylic acid having an ethylenically unsaturated group in the molecule. Epoxycarboxylate compound (A) obtained by reacting with compound (b), diisocyanate compound (B), polybasic acid anhydride (D), and diol compound compound (C) other than compound (A) as an optional component It is obtained by reacting with.

Epoxy compound (a) having two or more epoxy groups in the molecule used for producing the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention
Is particularly preferably an epoxy compound (a) having an epoxy equivalent of 100 to 900 g / equivalent. When the epoxy equivalent is less than 100, the molecular weight of the resulting aqueous alkaline solution-soluble polyester urethane compound (E) may be small and film formation may be difficult or flexibility may not be sufficiently obtained, and when the epoxy equivalent is more than 900. , A monocarboxylic acid having an ethylenically unsaturated group (b)
There is a risk that the introduction rate of the compound will decrease and the photosensitivity will decrease.

Specific examples of the epoxy compound (a) 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, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound, etc. Bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-
Bis (4-hydroxyphenyl) -1,1,1,3
Hydrogenated bisphenol type epoxy compound such as 3,3-hexafluoropropane epoxy compound, brominated bisphenol-A type epoxy resin, brominated bisphenol-
Halogenated bisphenol type epoxy compounds such as F type epoxy resins, alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compounds, 1,6-hexanediol diglycidyl ether,
Examples thereof include aliphatic diglycidyl ether compounds such as 1,4-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), DDR-331, DDR
-332, DDR-324 (all manufactured by Dow Chemical Co., Ltd.), Epicron 840, Epiclon 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide), 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-DGD (Maruzen Petrochemical Co., Ltd.), Lycaredin HBD
− Hydrogenated bisphenols such as 100 (manufactured by Shin Nippon Rika) −
A type epoxy resin, DDR-513, DDR-514,
Brominated bisphenol-A type epoxy resin such as DDR-542 (all manufactured by Dow Chemical Co., Ltd.), Celoxide 2021 (manufactured by Daicel), Licaredin DMD-100
(Nippon Rika), DX-216 (Nagase Kasei) and other alicyclic epoxy resins, DD-503 (Asahi Denka), Rikaresin W-100 (Nippon Rika), DX-212, D
FL-DP-5, aliphatic diglycidyl ether compounds such as X-214 and DX-850 (both manufactured by Nagase Kasei)
0, polysulfide type diglycidyl ether compound such as FLDP-60 (all manufactured by Toraythiocol), YX
Biphenol-type epoxy compounds such as -4000 (manufactured by Japan Epoxy Resin).

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for producing the aqueous alkaline solution-soluble polyester urethane compound (E) 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.

As the diisocyanate compound (B) used for producing the alkaline aqueous solution-soluble polyester urethane compound (E) of the present invention, any diisocyanate compound (B) having two isocyanate groups in the molecule can be used. Phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, which are particularly excellent in flexibility, etc. , Allyl cyan diisocyanate, N-acyl diisocyanate, trimethyl hexamethylene diisocyanate Isocyanate or lysine diisocyanate is preferable.

As the diol compound (C) other than the compound (A) used for producing the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention, two hydroxyl groups are bonded to two different carbon atoms. Any aliphatic or alicyclic compound can be used, and ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-heptanediol, 1,9-
Nonanediol, 1,10-decanediol, hydrobenzoin, benzpinacol, cyclopentane-1,2
-Diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, cyclohexane-1,
2-dimethanol, cyclohexane-1,4-dimethanol, spiroglycol, dimethylolpropionic acid,
Examples thereof include diol compounds such as dimethylolbutanoic acid, and reaction products of these diol compounds with oxides such as ethylene oxide and propylene oxide.

As the polybasic acid anhydride (D) used for producing the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention, any polybasic acid anhydride (D) can be used as long as it has at least two acid anhydride structures in the molecule. Pyromellitic dianhydride, ethylene glycol-bis can be used
(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 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 acid anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-c] furan-1,3
Particularly preferred are polybasic acid anhydrides selected from the diones.

The production of the alkaline aqueous solution soluble polyester urethane compound (E) of the present invention is carried out by reacting the above-mentioned epoxy compound (a) with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (hereinafter referred to as (Referred to as one reaction) to obtain an epoxycarboxylate compound (A) in which an alcoholic hydroxyl group is formed, and the epoxycarboxylate compound (A) is reacted with a diisocyanate compound (B) and a compound (C) as an optional component ( Hereinafter, this can be performed as an esterification reaction (hereinafter referred to as a third reaction) with a polybasic acid anhydride (D).

The alkaline aqueous solution-soluble polyester urethane compound (E) of the present invention comprises an epoxycarboxylate compound (A) having an alcoholic hydroxyl group formed by the first reaction and a polybasic acid anhydride (D). It can also be obtained by reacting (hereinafter referred to as the fourth reaction) and subjecting this to a urethanization reaction (hereinafter referred to as the fifth reaction) with the diisocyanate compound (B). At this time, the compound (C) can be reacted as an optional component.

The production of the alkaline aqueous solution-soluble polyester urethane compound (E) of the present invention is carried out by the first reaction after the reaction between the diisocyanate compound (B) and the compound (C) (hereinafter referred to as the sixth reaction). An esterification reaction (hereinafter referred to as a seventh reaction) can be performed with the epoxycarboxylate compound (A) having an alcoholic hydroxyl group formed and the polybasic acid anhydride (D).

The first reaction is solvent-free or a solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, ethyl methyl ketone and cyclohexanone, benzene, toluene, xylene, tetramethylbenzene and the like. 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 and solvent naphtha, and further crosslinking agents described later. It can be carried out in a single or mixed organic solvent such as (G).

The proportion of the raw materials charged in this reaction is 80 to 120 equivalent% of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, relative to 1 equivalent of the epoxy compound (a). preferable. If it deviates from this range, gelation may be caused during the second reaction, or the thermal stability of the finally obtained alkaline aqueous solution-soluble polyester urethane compound (E) 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 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:
Examples thereof include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate and the like.

The second reaction is a urethanization reaction in which, after the completion of the first reaction, the above-mentioned diisocyanate compound (B) is gradually added to the reaction solution and reacted as a dispersion or solution. At this time, the compound (C) can be reacted as an optional component. The reaction can be carried out without a catalyst, but a basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

The third reaction is an esterification reaction in which the polybasic acid anhydride (D) described above is added to the reaction solution after the completion of the second reaction and reacted as a dispersion or solution. The reaction can be carried out without a catalyst, but a basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

The fourth reaction is an esterification reaction in which the polybasic acid anhydride (D) is added to the reaction solution after completion of the first reaction and reacted as a dispersion or solution. The reaction can be carried out without a catalyst, but a basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

The fifth reaction is a urethanization reaction in which after the completion of the fourth reaction, the above-mentioned diisocyanate compound (B) is gradually added to the reaction solution and reacted as a dispersion or solution. At this time, the compound (C) can be reacted as an optional component. The reaction can be performed without a catalyst,
A basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

In the sixth reaction, the above-mentioned diisocyanate compound (B) is gradually added to the solution of compound (C) to prepare a dispersion liquid,
Alternatively, it is a urethanization reaction in which the solution is reacted. The reaction can be carried out without a catalyst, but a basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

The seventh reaction is an esterification reaction in which the aforementioned compound (A) and polybasic acid anhydride (D) are added to the reaction solution obtained in the sixth reaction and reacted as a dispersion or solution. . The reaction can be carried out without a catalyst, but a basic catalyst 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 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

With respect to the charged amount of each component, when the charged equivalent of the compound (A) in the second reaction is x equivalent and the charged equivalent of the compound (B) is y equivalent, the equivalent ratio is x> y.
It is preferably in the range of. Further, in the fourth reaction, the charged equivalent of the compound (A) is x'equivalent, the compound (D)
It is desirable that the equivalent ratio is in the range of x '>y', where y'is the charge equivalent. When the compound (C) is reacted as an optional component, z + x or z + x ′ is preferably a value exceeding y and y ′, where z is the charged equivalent amount of the compound (C). In the sixth reaction, when the charged equivalent of the compound (B) is x ″ equivalent and the charged equivalent of the compound (C) is y ″ equivalent, the equivalent ratio is preferably in the range of x ″ <y ”. In the third, fourth, and seventh reactions, as the polybasic acid anhydride (D), the solid acid value of the alkaline aqueous solution-soluble polyesterurethane compound (E) of the present invention is 50 to 150 mg · KOH / g. Such a calculated value is added, and the ratio of (the number of moles of compound (A) + compound (B) obtained in the second reaction) / (the number of moles of compound (D)) or (the fourth The ratio of (the number of moles of compound (A) + compound (D)) / (the number of moles of compound (B)) obtained in the reaction, (the compound (B) + obtained in the sixth reaction)
It is preferable to charge the mixture so that the ratio of (mol number of compound (C) + mol number of compound (A)) / (mol number of compound (D)) is in the range of 1 to 5. If this value is less than 1, an acid anhydride group will remain at the terminal of the alkaline aqueous solution-soluble polyester urethane compound (E) of the present invention, and the thermal stability is low and gelation may occur during storage. Not preferable. When this value exceeds 5, the molecular weight of the aqueous alkaline solution-soluble polyester urethane compound (E) 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. Further, when the solid content acid value exceeds 150 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 urethane compound (E), a photopolymerization initiator (F), a cross-linking agent (G), and a curing component (H) as an optional component. It is characterized by

The content ratio of the above-mentioned aqueous alkaline solution-soluble polyester urethane compound (E) used in the photosensitive resin composition of the present invention is usually 15 to 15 when the solid content of the photosensitive resin composition is 100% by weight. 70% by weight, preferably 20 to 60% by weight.

Specific examples of the photopolymerization initiator (F) 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-diethoxy-2-phenylacetophenone, 2,2
-Diethoxy-2-phenylacetophenone, 1,1-
Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyquinohexyl 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 benzyl dimethyl 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 (F)
On the other hand, the addition amount of 100% or less is preferable.

Specific examples of the crosslinking agent (G) 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, ε-caprolactone of neopentyl hydroxybivalate Di (meth) acrylate as an adduct (for example, KAY manufactured by Nippon Kayaku Co., Ltd.)
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 compound. (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 and (meth) acrylic Epoxy (meth) acrylate, which is a reaction product of an acid, and the like can be mentioned. The addition ratio of these is usually 2 to 40% by weight when the solid content of the photosensitive resin composition is 100% by weight,
It is preferably 5 to 30% by weight.

Examples of the curing component (H) used as an optional component in the photosensitive resin composition of the present invention include epoxy compounds and oxazine compounds. Curing component (H)
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 (H) include, for example, 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. D. 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.), DOCN-102S, DOCN-103.
S, DOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (made by Union Carbide), DSCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include DPPN-503 and DPPN-
502H, DPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Co.), Epicoat D1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Etc. Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon DXA-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. D. 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.

Examples of the biphenol type epoxy resin include 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 D
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 DXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Examples of the alicyclic epoxy resin include DHPD-
3150 (manufactured by Daicel Chemical Industries, Ltd.) and the like. Examples of the heterocyclic epoxy resin include TDPI
C, TDPIC-L, TDPIC-H, TDPIC-S
(Both manufactured by Nissan Chemical Industries, Ltd.) and the like.

Specific examples of the oxazine compound used as the curing component (H) 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 (H), an equivalent amount of 200 calculated from the acid value and the solid content of the alkali aqueous solution-soluble epoxycarboxylate compound of the present invention is 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.

Further, if necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay and the like filler, 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 above-mentioned curing component (H) may be mixed with the above resin composition in advance, but it may also be mixed before being applied to the printed wiring board. That is, the above-mentioned (E) component is the main component solution containing the epoxy curing accelerator and the like as the main component solution, and the curing agent solution containing the curing component (H) as the main component. It is preferable to use them as a mixture.

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 by a support film and a protective film.

The photosensitive resin composition (liquid or film form) of the present invention is used as a resist material such as an insulating material between layers of electronic parts, a solder resist for an optical waveguide or a printed circuit board connecting optical parts, 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 in 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 film thickness of this cured product layer is 0.5 to 160 μm.
It is 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 hydrogen carbonate, potassium hydrogen carbonate, 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.

[0049]

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 group in the molecule, and 2-methylhydroquinone as a thermal polymerization inhibitor. 0.24 g and 1.45 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.
The reaction was continued until the amount became equal to or less than / g to obtain an epoxycarboxylate compound (A) (theoretical molecular weight: 508.5). Next, 265.56 g of carbitol acetate as a reaction solvent and 0.44 g of 2-methylhydroquinone as a thermal polymerization inhibitor were added to this reaction liquid, and the temperature was raised to 60 ° C. Isophorone diisocyanate (molecular weight: 222.3) as a diisocyanate compound (B) was added to this solution.
1.15 g was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption around 2250 cm ⁻¹ disappeared by the infrared absorption spectrum measurement method. Polybasic acid anhydride (D) was added to this solution as a product of MC DuPont P
MDA (pyromellitic anhydride (molecular weight: 218.1))
54.53 g, carbitol acetate 97.46 g,
2-Methylhydroquinone as a thermal polymerization inhibitor is 0.5
2 g was added. After the addition, the temperature was raised to 95 ° C. and the reaction was carried out for 6 hours to obtain a resin solution containing 65% by weight of the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention (this solution is referred to as E-1). When the acid value was measured,
27.05 mg KOH / g (solid content acid value: 41.61)
mg · KOH / g).

Example 2 In a 2 L flask equipped with a stirrer and a reflux tube,
An epoxy compound (a) having two or more epoxy groups,
Then, Nippon Kayaku RE-310S (bifunctional bispheno
-A type epoxy resin, epoxy equivalent: 183.5 g
/ Equivalent) 367.0 g, ethylenically unsaturated group in the molecule
Acrylic acid as the monocarboxylic acid compound (b) having
(Molecular weight: 72.06) 144.1 g, thermal polymerization inhibitor
As hydroquinone monomethyl ether 1.02g
And triphenylphosphine as a reaction catalyst at 1.5
Charged 3 g, the acid value of the reaction solution was 0.5 mg at a temperature of 98 ° C.
・ React until KOH / g or less, epoxy carbo
Xylate compound (A) (theoretical molecular weight: 511.1)
Obtained. Then, add carbitol as a reaction solvent to the reaction solution.
445.93 g of luacetate, 2 as a thermal polymerization inhibitor
-0.70g of methyl hydroquinone, optional geo
Dimethyl compound (C) as dimethylolpropionic acid (min
Addition amount: 134.1) (118.8 g) was added and the temperature was raised to 60 ° C.
Let Diisocyanate compound (B) was added to this solution.
Trimethylhexamethylene diisocyanate (molecule
Amount: 210.28) 198.3 g of reaction temperature of 65 ℃
It was dripped gradually so as not to exceed it. After dropping, the temperature is set to 8
Raise the temperature to 0 ° C and measure 2
250 cm ^-1Reacts for 6 hours until absorption in the vicinity disappears
Let To this solution, as polybasic acid anhydride (D),
-PMDA (pyromellitic anhydride (min
Volume: 218.1)) 79.9 g, carbitol acete
43.0 g was added. After addition, raise the temperature to 95 ° C
Then, the mixture is allowed to react for 6 hours.
Resin containing 65 wt% of reester urethane compound (E)
A solution was obtained (this solution is designated as E-2). Measure the acid number
When found, 66.61 mg · KOH / g (solid content acid value:
It was 102.48 mgKOH / 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: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. ) To 14
4.1 g, 1.10 g of hydroquinone monomethyl ether 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. The reaction was continued until it became an epoxycarboxylate compound (A) (theoretical molecular weight: 548.2). Next, 355.03 g of methyl ethyl ketone as a reaction solvent and 2.03 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor were added to this reaction liquid, and the temperature was raised to 60 ° C. 111.15 g of isophorone diisocyanate (molecular weight: 222.3) as a diisocyanate compound (B) was gradually added dropwise to this solution so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption around 2250 cm ⁻¹ disappeared by the infrared absorption spectrum measurement method. In this solution, as polybasic acid anhydride (D), 54.53 g of PMDA (pyromellitic anhydride (molecular weight: 218.1)) manufactured by MC DuPont, 29.37 g of methyl ethyl ketone, and hydroquinone monomethyl ether as a thermal polymerization inhibitor were added. .20 g was added. After the addition, the temperature was raised to 95 ° C. and the reaction was carried out for 6 hours to obtain a resin solution containing 65% by weight of the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention.
-3). When the acid value was measured, it was 25.54 mg.
・ KOH / g (acid value of solid content: 39.30 mg ・ KOH /
g).

Example 4 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) was used.
Functional bixylenol type epoxy resin, epoxy equivalent: 1
396.0 g of 96.0 g / equivalent), 144.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and 2 as a thermal polymerization inhibitor. 0.27 of methyl hydroquinone
and triphenylphosphine as a reaction catalyst.
61 g were charged, and the acid value of the reaction solution was 0.5 m at a temperature of 98 ° C.
Epoxycarboxylate compound (A) (theoretical molecular weight: 536.1) by reacting until g · KOH / g or less
Got Next, 332.6 g of carbitol acetate as a reaction solvent and 2 as a thermal polymerization inhibitor were added to the reaction solution.
-0.475 g of methylhydroquinone, PMDA (pyromellitic dianhydride (molecular weight: 218.1)) manufactured by MC DuPont as polybasic acid anhydride (D) 109.1
g was added. After the addition, the temperature was raised to 95 ° C. and the reaction was performed for 6 hours. Add carbitol acetate 23.
After adding 40 g and 0.509 g of 2-methylhydroquinone as a thermal polymerization inhibitor and setting the temperature of the solution to 65 ° C.,
To this solution, as the diisocyanate compound (B), tolylene diisocyanate (molecular weight: 174.2) 43.55
g was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature is raised to 80 ° C., and the reaction is allowed to proceed for 6 hours until the absorption around 2250 cm ⁻¹ disappears by the infrared absorption spectrum measurement method, and 65% by weight of the alkaline aqueous solution-soluble polyester urethane compound (E) of the present invention is added. A containing resin solution was obtained. When the acid value was measured, it was 55.1.
9 mg · KOH / g (solid content acid value: 84.91 mg · K
OH / g).

Example 5 RE-310S (bifunctional bisphenol-A manufactured by Nippon Kayaku Co., Ltd.) was used as an epoxy compound (a) having two or more epoxy groups in the molecule in a 2 L flask equipped with a stirrer and a reflux tube. Type epoxy resin, epoxy equivalent: 183.5g
/ Equivalent) 367.0 g, 144.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl ether as a thermal polymerization inhibitor 1 .02g
And triphenylphosphine as a reaction catalyst at 1.5
Charged 3 g, the acid value of the reaction solution was 0.5 mg at a temperature of 98 ° C.
-It was made to react until it became below KOH / g, and the epoxy carboxylate compound (A) (theoretical molecular weight: 511.1) was obtained. Separately from this reaction solution, 118.8 g of dimethylolpropionic acid (molecular weight: 134.1) as a diol compound (C) other than the compound (A) and 170.7 g of carbitol acetate as a reaction solvent were subjected to thermal polymerization. As an inhibitor, 0.24 g of 2-methylhydroquinone was added and the temperature was raised to 60 ° C. To this solution, 198.3 g of trimethylhexamethylene diisocyanate (molecular weight: 210.3) as a diisocyanate compound (B) was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After the dropping is completed,
The temperature was raised to 80 ° C. and the reaction was carried out for 6 hours until the absorption around 2250 cm ⁻¹ disappeared by the infrared absorption spectrum measurement method. 511.1 g of the above epoxycarboxylate compound (A) and polybasic acid anhydride (D) were added to this solution.
As PMDA, 79.9 g of PMDA (pyromellitic anhydride (molecular weight: 218.1)) manufactured by MC DuPont, 318.3 g of carbitol acetate, and 0.70 g of 2-methylhydroquinone as a thermal polymerization inhibitor were added. After the addition, the temperature was raised to 95 ° C. and the reaction was carried out for 6 hours to obtain a resin solution containing 65% by weight of the aqueous alkaline solution-soluble polyester urethane compound (E) of the present invention. When the acid value was measured, it was 65.20 mg · KOH / g (solid content acid value:
It was 100.31 mgKOH / g).

Examples 6 and 7 (E-1) and (E-2) obtained in Examples 1 and 2 were mixed in the mixing ratio shown in Table 1 and, if necessary, kneaded with 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 a step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film, and the cumulative light amount was 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 subjected to an acidic degreasing solution (MDtDx 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 whether or not there was an abnormality in the 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

[0071] Table 1                                       Example Note 6 7 Resin solution   E-1 51.80   E-2 51.80 Cross-linking agent (G)   DPCA * 1 3.38   HX-220 * 2 3.38 Photopolymerization initiator (F)   Irgacure 907 * 3 4.50 4.50   DDTX-S * 4 0.45 0.45 Curing component (H)   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 * 8 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 JDR: Bifunctional bixylenol type epoxy resin * 6 BYK Chemie: Leveling agent * 7 Shin-Etsu Chemical Product: Defoamer * 8 Solvent: Carbitol acetate

Table 2 Example 67 Evaluation item Tackiness ○ ○ Developability ○ ○ Resolution ○ ○ Light sensitivity 12 11 Surface gloss ○ ○ Substrate sled ○ △ Flexibility ○ ○ Adhesion ○ ○ Pencil hardness 4H 5H Solvent resistance ○ ○ Acid resistance ○ ○ Heat resistance ○ ○ Gold plating resistance ○ ○ PCT resistance ○ ○ Thermal shock resistance ○ ○

Example 8 54.44 g of the resin solution (E-3) obtained in Example 3,
As a cross-linking agent (G), HX-220 (trade name: bifunctional acrylate resin manufactured by Nippon Kayaku) 3.54 g, and as a photopolymerization initiator (F), Irgacure 907 (trade name: photopolymerization initiator manufactured by Bantico) 4.72g and Kayacure D
DTX-S (trade name: photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.) was used.
47 g, YX-8000 (trade name: Japan Epoxy Resin, bifunctional hydrogenated bisphenol-A type epoxy resin, epoxy equivalent: 202.06) as a curing component (H)
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 subjected to 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 using a ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern (irradiation amount 500 mJ / square centimeter). 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 clear from the above results, the alkaline aqueous solution-soluble polyester urethane 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. , Excellent in chemical resistance, gold plating resistance, and the like, cracks do not occur on the surface of the cured product, and even when a thin film substrate is used, it is a photosensitive resin composition for a printed circuit board with less warpage. it is obvious.

[0078]

INDUSTRIAL APPLICABILITY An alkaline aqueous solution-soluble polyester urethane 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 rays, and the resulting cured product is obtained. Is flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance,
Gold plating resistance and the like are also sufficiently satisfied, and are particularly suitable for a photosensitive resin composition for printed wiring boards and a photosensitive resin composition for forming an optical waveguide.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 TF term (reference) 2H025 AA06 AA07 AA08 AA10 AA13 AA14 AB15 AC01 AD01 BC67 BC74 BC83 CA00 CC17 FA17 4J034 BA02 BA06 CA04 CA26 CA34 CB03 CB04 CB05 CB08 CC03 CC12 CC26 CC38 CD08 CD14 DK02 DK05 DK06 DK08 FA02 FB01 FC02 FD03 FD07 HA07 HB02 HB05 HC23 HC14 JA21 JA01 K14 JA12 JA14 K01 JA12 K14 JA21 JA14 K01 JA23 K14 JA02 JA21 K14 JA12 JA14 C02 HC14 KD25 KE02 QC03 RA14 SA02 SA08 SB01 SB03 5E314 AA27 AA32 CC07 CC15 DD07 GG11 GG14 5E343 AA18 BB24 BB67 CC63 ER12 ER16 ER18 GG03 5E346 AA12 CC09 CC32 DD02 DD03 HH11 HH13

Claims (19)

[Claims] 1. An aqueous alkaline solution-soluble polyester urethane compound (which is obtained by reacting the following compound (A), compound (B), compound (D), and optionally compound (C): E). Compound (A): Epoxycarboxylate compound compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (B): diisocyanate compound compound (C): diol compound other than compound (A) compound (D): polybasic acid anhydride. 2. An epoxycarboxylate compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule ( Polyester of (A), diisocyanate compound (B), and diol compound (C) as an optional component is reacted with polybasic acid anhydride (D), and the aqueous alkaline solution-soluble polyester according to claim 1. Method for producing urethane compound (E). 3. An epoxycarboxylate compound (which is obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule ( The charge equivalent of A) is x
Equivalent, the charged equivalent of the diisocyanate compound (B) is y
The method for producing an aqueous alkaline solution-soluble polyester urethane compound (E) according to claim 1, wherein the equivalent ratio is x> y when the equivalent is defined. 4. An epoxycarboxylate compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule ( The method for producing an aqueous alkaline solution-soluble polyester urethane compound (E) according to claim 1, wherein the diisocyanate compound (B) is reacted after the reaction with A) and the polybasic acid anhydride (D). 5. An epoxycarboxylate compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule ( The equivalent ratio is x '>y' when the charged equivalent of A) is x'equivalent and the charged equivalent of polybasic acid anhydride (D) is y'equivalent, and the equivalent ratio is x '>y'. Item 4. A method for producing the aqueous alkaline solution-soluble polyester urethane compound (E) according to the item. 6. An epoxy compound (a) having two epoxy groups in the molecule and a monocarboxylic acid having an ethylenically unsaturated group in the molecule after the reaction of the diisocyanate compound (B) and the diol compound (C). The epoxy carboxylate compound (A) obtained by reacting with the compound (b) is reacted with a polybasic acid anhydride (D), and the aqueous alkaline solution-soluble polyester urethane compound (E) according to claim 1. Manufacturing method. 7. The equivalent ratio is x ″ <y ”when the charged equivalent of the diisocyanate compound (B) is x ″ equivalent and the charged equivalent of the diol compound (C) is y ″ equivalent.
Alternatively, the method for producing the aqueous alkaline solution-soluble polyester urethane compound (E) according to claim 6. 8. The epoxy equivalent of the epoxy compound (a) having two epoxy groups in the molecule is 100 to 900 g /.
The alkaline aqueous solution-soluble polyester urethane compound (E) according to any one of claims 1 to 7, which is an equivalent amount of an epoxy compound. 9. 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 to 8, which is an epoxy compound selected from an aliphatic diglycidyl ether compound, a polysulfide type diglycidyl ether compound, a biphenol type epoxy compound or a bixylenol type epoxy compound. Aqueous solution soluble polyester urethane compound (E). 10. A monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is (meth) acrylic acid,
The reaction product of (meth) acrylic acid and ε-caprolactone or a monocarboxylic acid selected from cinnamic acid is an aqueous alkaline solution-soluble polyester urethane compound according to any one of claims 1 to 9. E). 11. A diisocyanate compound (B) is a phenylene diisocyanate, a tolylene diisocyanate,
Xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate,
The aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of claims 1 to 10, which is a compound selected from allyl cyan diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate or lysine diisocyanate. 12. A photosensitive resin containing the aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of claims 1 to 11, wherein the hydroxyl group of the diol compound (C) is an alcoholic hydroxyl group. 13. The polybasic acid anhydride (D) is pyromellitic dianhydride, 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 dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride,
3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxy) Phenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic acid anhydride, 3a, 4,5,9b-tetrahydro-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
The alkaline aqueous solution-soluble polyester urethane compound according to any one of claims 1 to 12, which is a polybasic acid anhydride selected from naphtho [1,2-c] furan-1,3-dione. E). 14. The acid value of solid content is 30 to 150 mg · KO.
The aqueous alkaline solution-soluble polyester urethane compound (E) according to any one of claims 1 to 13, which has a H / g. 15. A photosensitive resin composition containing the aqueous alkaline solution-soluble polyester compound (E) according to any one of claims 1 to 14. 16. A photosensitive resin composition according to claim 15, which comprises a photopolymerization initiator (F), a crosslinking agent (G) and a curing component (H) as an optional component. Resin composition. 17. A cured product of the photosensitive resin composition according to claim 15 or 16. 18. A substrate having a layer of the cured product according to claim 17. 19. An article having the substrate according to claim 18.