JPH0497362A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a coating film with high sensitivity to exposure to ultraviolet rays and with less tackiness and to be excellent in the developing property in an alkaline aqueous solution by reacting a polyglycidyl ether compound obtain from a bisphenol-S derivative, an unsaturated monocarboxylic acid and a polybasic anhydride successively. CONSTITUTION:This composition incorporates a photopolymerized compound being obtained from reacting successively the polyglycidyl ether compound obtained from the bisphenol-S derivative, the unsaturated monocarboxylic acid and the polybasic anhydride, and a photoradical polymerization initiator. Thus the coating film with high sensitivity to exposure by ultraviolet rays and with less tackiness is obtained and it is excellent in the developing property in an alkaline aqueous solution, and excellent in the heat resistance of the hardened film, the adhesive strength with a supporting base, and the electrical characteristics, and it is most suitable to a protective film of a colored filter layer and electron devices and a permanent protective mask, etc., for solder resists for manufacturing printing circuit board, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a photocurable resin composition, and more specifically,
The coating film is highly sensitive to ultraviolet light exposure, has low tackiness, and has excellent developability in alkaline aqueous solutions.The cured film also has excellent heat resistance, adhesion to substrates, and electrical properties, making it ideal for color filter layers and electronics. The present invention relates to a photocurable resin composition that is optimal for uses such as protective films for devices and permanent protective masks such as solder resists for manufacturing printed wiring boards.

(Prior Art) Various fields of use have been developed for photocurable resin compositions. Among them, there are applications in which patterning is possible by exposure and development, and the cured film is required to have heat resistance.

Examples include permanent protective masks such as solder resists for manufacturing printed wiring boards. The main purpose of solder resist is to limit the soldering area, prevent solder bridges, prevent corrosion of conductors, and maintain electrical insulation between conductors over a long period of time. . Conventionally, this solder resist was produced by a printing method, but as printed wiring boards become finer patterns, photocurable resin compositions are being used. The solder resist may be in the form of a dry film or a liquid resin composition, with the latter being the most common.

Examples of this include JP-A-62-7773 and JP-A-62-7773.
There is a photocurable resin composition containing a photopolymerizable compound obtained by reacting a novolac type epoxy compound and an unsaturated monocarboxylic acid as disclosed in Japanese Patent No. 7774.

Furthermore, in recent years, due to problems such as work environment, air pollution, and water pollution, a photocurable resin composition that can be developed with an alkaline aqueous solution or water has been desired. An example of this is the Japanese Unexamined Patent Publication No. 6
1-243869, 63-258975, etc., a light containing a photopolymerizable compound obtained by sequentially reacting a novolac type epoxy compound, an unsaturated monocarboxylic acid, and a polybasic acid anhydride. There are curable resin compositions.

As for other uses, with the development of color liquid crystal panels, there is an increasing demand for it as a protective film for color filters. The main purpose of the color filter's protective film is to increase the accuracy of the thickness of the liquid crystal layer, making it transparent 11! The purpose is to flatten the surface of the upper part of the color filter layer so as not to cause disconnection when providing the electrodes, but it is necessary to have heat resistance to high temperature treatment to lower the resistance of the transparent electrode. Such techniques are disclosed in Japanese Unexamined Patent Publications Nos. 2-72302, 2-101404, and the like. As the protective film used in this case, it is described that a non-photosensitive resin such as an acrylic resin, a polyimide resin, a polyolefin resin, a thermosetting acrylic resin, or a photosensitive acrylic resin is applied.

Among them, photocurable resins that cure by light irradiation do not require heating after light irradiation or are easily cured by heating at relatively low temperatures, so processing time can be shortened, and color filter layers can be cured easily. This is particularly suitable because it can prevent deterioration of itself during curing. Furthermore, the protective film of the color filter may require patterning. Such a technique is disclosed in Japanese Unexamined Patent Publication No. 59-184325 and the like. As the protective film used in this case, a coating of photocurable polyvinyl alcohol or the like is described. Even in such cases, the method using a photocurable resin has the advantage that high-resolution patterning is easier than the method of printing a non-photosensitive resin. In this case as well, it is desirable to be able to develop with an alkaline aqueous solution or water due to problems such as working environment, air pollution, and water pollution.

However, the photocurable resins known so far have problems such as insufficient heat resistance with photocurable acrylic resins and photocurable botavinyl alcohol, and insufficient coating suitability and developability with photocurable polyimide resins. On the other hand, the above-mentioned photocurable modified epoxy resin has sufficient performance. However, as disclosed in the most common Japanese Patent Application Laid-open Nos. 61-243869 and 63-258975,
Novolak type epoxy compound, unsaturated monocarboxylic acid,
In the case of photopolymerizable compounds obtained by sequentially reacting polybasic acid anhydrides, the basic skeleton is a rigid novolac type epoxy compound, and α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid are used as unsaturated monocarboxylic acids. Only examples of saturated monocarboxylic acids are disclosed.

Therefore, the resulting photopolymerizable compound has lower sensitivity than ordinary photopolymerizable monomers, requiring a long exposure time and reducing workability. Alternatively, there are problems such as damage to the photomask due to temperature rise during exposure.

Therefore, in order to solve these three points,
No. 253729 and No. 2-43551 disclose a method in which a (meth)acrylate half-ester having a hydroxyl group of a dibasic acid is used alone or as a mixture with (meth)acrylic acid as the unsaturated monocarboxylic acid, and acrylic acid. A photocurable resin composition containing a photopolymerizable compound obtained by a method using a dimer or the like has been proposed.

However, even when these photopolymerizable compounds are used, the sensitivity is still not sufficient. Further, similar descriptions of photopolymerizable compounds can be found in JP-A-1-141904, but there is no particular mention of the effects of using these photopolymerizable compounds.

On the other hand, in JP-A-1-296240 and JP-A-1-303429, etc., the above-mentioned novolac type epoxy compound is used as bisphenol A diglycidyl ether, naphthalene diglycidyl ether, etc., and (meth)
It has been described that a photopolymerizable compound obtained by sequentially reacting acrylic acid and a polybasic acid anhydride is used;
Even in these cases, no particular improvement in sensitivity was observed.

(Problems to be Solved by the Invention) The objects of the present invention are to obtain a coating film that is highly sensitive to ultraviolet light exposure, has low tackiness, has excellent developability in an alkaline aqueous solution, and has good heat resistance and The object of the present invention is to provide a photocurable resin composition that has excellent adhesion to a substrate and excellent electrical properties.

(Means for Solving the Problems) The purpose of the present invention is to (A) (1) sequentially react a polyglycidyl ether compound obtained from a bisphenol S derivative, ■ an unsaturated monocarboxylic acid, and ■ a polybasic acid anhydride. This was achieved using a photocurable resin composition containing the photopolymerizable compound obtained by the above method and (B) a photoradical polymerization initiator.

Typical polyglycidyl ether compounds obtained from bisphenol S derivatives have the following general formula (
1).

General formula (1) % formula %) Here, A r + + A r 2 + A r 3
1 A r a is phenylene or substituted phenylene,
n is an integer of 1 to 5, and m is O or an integer of 1 or more.

Ar+, Ar2. Ar3. Examples of Ara include phenylene, or phenylene substituted with an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or phenylene substituted with an alkenyl group such as a vinyl group or allyl group, or a phenylene substituted with a chloro group or a bromo group. Examples include phenylene substituted with a halogen group such as a phenylene group, a phenylene substituted with a hydroxy group, an alkoxy group, etc. These can be used alone or in combination
You can mix more than one species. These are commercially available products such as Evicron EXA1514 manufactured by Dainippon Ink Co., Ltd.

As the unsaturated monocarboxylic acid, a compound represented by the following general formula () is preferable.

General formula (11) %Formula% Here, R1 represents a hydrogen atom or a methyl group, and R2 represents a divalent organic group not containing a carboxyl group.

Preferred examples of R include alkylene, substituted alkylene, phenylene, substituted phenylene, aralkylene,! Examples include substituted aralkylenes, those containing esters, ethers, ketones, thioethers, etc., or combinations thereof. Specifically, ring-opening reaction products of dimer, trimer or higher oligomer (meth)acrylic acid and cyclic ester such as caprolactone by Michael addition of (meth)acrylic acid, hydroxyalkyl (meth)acrylate Ester, trimethylolpropane (
A monoesterification reaction product of a (meth)acrylate having a hydroxy group such as meth)acrylate, pentaerythritol tri(meth)acrylate, or glycerin di(meth)acrylate with a dibasic acid anhydride; Preferred examples include reaction products of meth)acrylates and halogen-containing carboxylic acid compounds.

Among these, commercially available products include 70Nix M-5300 manufactured by Toagosei Kagaku Kogyo Co., Ltd.
M-5400, M-5500 and M-5600, NK ester CB-1 and CB manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
HOA-MP and HOA-MS manufactured by XL Kyoeisha Yushi Kagaku Kogyo Co., Ltd., and Visco-manufactured by Osaka Organic Chemical Industry Co., Ltd.
Toga 2100 or the like can be used. Particularly preferably 70 nyx M-5400 manufactured by Toagosei Chemical Industry Co., Ltd.
, M-5600.

Further, as the unsaturated monocarboxylic acid, α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid, itaconic acid, and cinnamic acid can also be used.

An unsaturated monocarboxylic acid represented by general formula (11) and α,
A β-unsaturated monocarboxylic acid may be used in combination. The reaction order in this case is that even if the unsaturated monocarboxylic acid represented by the general formula (11) and the α,β-unsaturated monocarboxylic acid are used simultaneously, the unsaturated monocarboxylic acid represented by the general formula (11) may come first or after. In this case, the molar ratio of the unsaturated monocarboxylic acid represented by the general formula (11) to the α,β-unsaturated monocarboxylic acid is 100:0 to 10:90, preferably 100:0 to 20:80. . When the molar ratio of α,β-unsaturated monocarboxylic acid exceeds 90, sensitivity tends to decrease.

Typical polybasic acid anhydrides include succinic anhydride, methylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, ethylsuccinic anhydride, and dodecenylsuccinic anhydride. Acid anhydride, nonenylsuccinic anhydride, maleic anhydride, 2.3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2
, 3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromo Phthalic anhydride, hexahytophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahytophthalic anhydride, endomethylenetetrahyphthalic anhydride, methylendomethylenetetrahydrophthalic anhydride,
Chlorendic anhydride and dibasic acid anhydrides such as 5-(2,5-dioxotetrahydrofuryl)-3-cyclohexene-12-dicarboxylic anhydride, glutaric anhydride, trimellitic anhydride, 3゜3 Polybasic acid anhydrides such as 4.4-benzophenone tetracarboxylic anhydride can be used, and particularly preferred are tetrahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

The photopolymerizable compound of the present invention is obtained by sequentially reacting the above three types of compounds, and the ratio at which they are reacted is as follows: General formula (11
), α, β-unsaturated monocarboxylic acid, or a mixture of unsaturated monocarboxylic acid and α, β-unsaturated monocarboxylic acid represented by general formula (II), in which the carboxyl group is 0. .5 to 1.2 equivalents, preferably 0.8 to 1.1 equivalents, and the polybasic acid anhydride is 0.1 to 1.2 equivalents.
1.1 equivalent, preferably 0.3 to 1.0 equivalent.

If the ratio of carboxyl groups is less than 0.5 equivalents, a decrease in sensitivity and gelation of the resin will occur, and if it exceeds 1.2 equivalents, problems with tackiness will occur.

Moreover, polybasic acid anhydride is 0. If the amount is less than 1 equivalent, the developability will deteriorate, and if it exceeds 1.1 equivalents, problems such as stickiness and crystal precipitation will occur.

These photo-uniform compounds can be used in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the solid content of the photocurable resin composition.

Examples of the photoradical 1 initiator used in the present invention include α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and thioxanthone. ,2,
Thioxanthone such as 4-diethylthioxanthone, thioxanthone-1-sulfonic acid, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4°-bis(diethylamino)benzophenone, etc. Benzophenones, acetophenone, p-dimethylaminoacetophenone, α
, α°-dimethoxyacetoxyacetophenone, 2.
2'-dimethoxy-2-phenylacetophenone, p-
Acetophenones such as methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl-2-morpholino-1-propanone, and 7-nthraquinone, 1゜4-
Quinones such as naphthoquinone, phenansyl chloride,
Tribromomethylphenylsulfone, tris(trichloromethyl)-S-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxydiphenyl)triazine, compounds described in JP-A-63-153542, etc. Examples include halogen compounds and peroxides such as di-t-butyl peroxide. Particularly preferred are 2,2'-dimethoxy-2-phenylacetophenone, 2-methyl-[
4-(methylthio)phenyl-2-morpholino-1
-Propanone (trade name: Coilgacure 907, manufactured by Ciba Geigy).

These photoradical polymerization initiators may be used alone or in combination of two or more. Examples of such a mixture of two or more types include a combination of 2,4.5-triarylimidazole dimer and 2-mercaptobenzoxazole or leuco crystal violet, and US Pat. No. 3427
combinations of 4,4'-bis(dimethylamino)benzophenone and benzophenone or benzoin methylethyl as described in US Pat.
-Combination with bis(trichloromethyl)-6-(4-methoxyphenyl)triazine, JP-A-57-236
Combination of dimethylthioxanthone and 4-dialkylaminobenzoic acid ester described in No. 02, JP-A-59
Examples include combinations of 4,4°-bis(dialkylamino)benzophenone, ketones, and trihalogenated methyl-containing compounds described in No. 78339.

The total amount of these photoradical polymerization initiators is preferably 0.1 to 30 parts by weight, particularly 0.1 to 30 parts by weight based on the photopolymerizable compound.
Preferably, 15 to 15 parts by weight are used. If it is less than 0.1 part by weight, the sensitivity decreases, and if it exceeds 30 parts by weight, precipitation of crystals, insufficient hardening of the lower part, etc. occur.

The photocurable resin composition of the present invention comprises the above-mentioned photopolymerizable compound,
In addition to the photoradical polymerization initiator, it is preferable to blend a polymerizable compound having at least one ethylenically unsaturated double bond and an epoxy compound having at least one epoxy group depending on the purpose of use. Furthermore, if necessary, a thermal curing accelerator, an organic solvent, etc. that cause the epoxy group to undergo a thermal reaction may be added.

Examples of the polymerizable compound having at least one ethylenically unsaturated double bond include esters of (meth)acrylic acid of monohydric or polyhydric alcohols.

Examples of the monohydric alcohol in the ester of (meth)acrylic acid of a monohydric or polyhydric alcohol include methanol, ethanol, propatool, isoproptool, n
-Butanol, isobutanol, t-butanol, cyclohexyl alcohol, benzyl alcohol, octyl alcohol, 2-ethylhexanol, lauryl alcohol, n-decanol, undecanol, cetyl alcohol, stearyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, butoxyethyl alcohol , polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, 2-hydroxy-3-chloropropane, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, glycidol, 2-trimethoxysilylethanol, ethylene chlorohydrin, ethylene bromohydrin, 2, 3-Jib O
Examples include mubropanol, allyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol, naphthol, and the like. In addition, as a polyhydric alcohol,
For example, ethylene glyfur, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, hexanediol, heptanediol, octanediol, nonanediol, dodecanediol, neopentyl Glycol, 1°10-
Decanediol, 2-butene-1,4-diol, 2-
n-butyl-2-ethylpropanediol, cyclohebutanediol, 1,4-cyclohebosandimethatol,
3-cyclohexene-1,1-jetanol, polyethylene glycol (diethylene glycol, triethylene glycol, etc.), polypropylene glycol (dipropylene glycol, tripropylene glycol, etc.), polystyrene oxide glycol, polytetrahydrofuran glycol, xylylene diol, bis(β- hydroxyethoxy)benzene, 3-chloro-1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2
, 2-diphenyl-1,3-propanediol, decalindiol, 1,5-dihydroxy-1,2,3,4-
Tetrahydronaphthalene, 2,5-dimethyl=2.5-
Hexanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-(hydroxymethyl)-1,3
-propanediol, 2-ethyl-2-methyl-1,3
-Propanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, 2-methyl-1,4
-butanediol, 2-methyl-2,4-bentanediol, 1-phenyl-1,2-ethanediol, 2゜2
．． 4.4-tetramethyl-1,3-cyclobutanediol, 2,3,5.6-tetramethyl-p-xylene-α
, α-diol, 1. i, 4゜4-tetraphenyl-
2-butyne-1,4-diol, 1,1-bi-2-naphthol, dihydroxynaphthalene, 1,1-methylene-
Di-2-naphthol, biphenol, 2,2-bis(4
-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, resorcinol, 2-
Methylresorcinol, 4-chlororesorcinol, bio-gallol, α-(1-7minoethyl)-p-hydroxybenzyl alcohol, 2-amino-2-methyl-1,
3-propanediol, 2-amino-2-ethyl-1,
3-propanediol, 3-amino-1,2-propanediol, N-(3-aminopropyl)-getanolamine, N,N'-bis(2-hydroxyethyl)
Piperazine, 1,3-bis(hydroxymethyl)urea, 1,2-bis(4-pyridyl)-1,2-ethanediol, N-n-butylgetanolamine, jetanolamine, N-ethylgetanolamine , 3-mercapto-1゜2-propanediol, 3-piperidine-1
, 2-propanediol, 2-(2-pyridyl)-1゜3-propanediol, α-(1-aminoethyl)-p
-Hydroxybenzyl alcohol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, α-mannitol, butanetriol, 1,2,6-1-dihydroxyhebeef san, 1.2.4-benzenetriol, triethanolamine, 2.2-bis(hydroxymethyl)-
2,2°, 2″-nitrilotriethanol, etc. Among these esters of (meth)acrylic acid of monohydric or polyhydric alcohols, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Preferred are trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, sorbitol hexa(meth)acrylate, sorbitol penta(meth)acrylate, etc. Particularly preferred is dipentaerythritol hexa(meth)acrylate.

It is also possible to use (meth)acrylamides of monoamines or polyamines. Examples of monoamines include ethylamine, butylamine, amylamine, hexylamine, octylamine, cyclohexylamine, monoalkylamines such as 9-7 minodecalin, monoalkenylamines such as allylamine, metaallylamine, and benzylamine, and aniline, toluidine, Aromatic amines such as p-aminostyrene can be mentioned. Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine,
Hexamethylenediamine, octamethylenediamine, hexamethylenebis(2-7minobrovir)amine, diethylenetriamine, triethylenetetraamine, polyethylenepolyamine, tris(2-7minoethyl)amine, 4.4゛-methylenebis(cyclohexylamine),
N,N'-bis(2-7minoethyl)-1°3-propanediamine, N,N'-bis(3-7minobrovir)-1,4-butanediamine, N.

No-bis(3-7minobrovir)ethylenediamine,
N,N'-bis(3-7minobrovir)-1,3-propanediamine, 1,3-cyclohexanebis(methylamine), phenylenediamine, xylylenediamine, β
-(4-7minophenyl)ethylamine, diaminotoluene, diaminoanthracene, diaminonaphthalene, diaminostyrene, methylene dianiline, 2,4-his(
Examples include 4-7minobenzyl)aniline, aminophenyl ether, and the like.

Furthermore, allyl compounds such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, benzoic acid, chlorobenzoic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid ,
Mono- or polyallyl esters of mono- or polycarboxylic acids such as chlorendic acid and trimellitic acid, mono- or diallyl esters of disulfonic acids such as benzenedisulfonic acid and naphthalenedisulfonic acid, diallylamine, N
N'-diallyl oxalic acid diamide, 1,3-diallylurea, diallyl ether, triallyl isocyanurate, etc. can also be used.

Also, for example, divinylbenzene, p-allylstyrene,
Polyvinyl compounds such as p-isopyrobenylstyrene, divinyl sulfone, ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl phthalate, divinyl phthalate, dihinyl terephthalate, etc., 2
Ester compounds of (meth)acrylic acid having an ionic group such as -hydroxy 3-(meth)acryloyloxypropyltrimethylammonium chloride and (meth)acryloyloxyphenyltrimethylammonium chloride can also be used.

Furthermore, commercially available polymerizable monomers or oligomers, such as 70nix M5700 and M61 manufactured by Toagosei Chemical Industry Co., Ltd.
00, M8O30, M152, M2O3, M215, M
Acrylate monomers such as 315 and M325, NK ester 2G, 4G, 9G, and 14G manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
,ABPE=4,A-TMPT,U-4HA,CB-1
, CBX-1, KAYARAD R60 manufactured by Nippon Kawara Co., Ltd.
4, DPCA-30, DPCA-60, K AYAMA
RPM-1, PM-2, San Nobuco Photomer 40
(meth)acrylate monomers such as 61.5007,
Lipoxy VR60, VR90, 5P15 manufactured by Showa Kobunshi Co., Ltd.
09 grade Noeboxy acrylate, Subirac E- manufactured by the same company
Spirane resins having a spiroacetal structure and a (meth)acrylic group such as 4000X and U3000 can also be used.

These compounds may be used alone or in a mixture of two or more, and may be used in an amount of 1 to 40 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the solid content of the photocurable resin composition. can.

Examples of epoxy compounds having at least one epoxy group include glycidyl ethers of alcohols having 2 to 20 carbon atoms, such as butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, aryl glycidyl ether, and phenyl glycidyl ether; Glycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycerol triglycidyl ether , polyglycidyl ethers of polyols such as trimethylolpropane triglycidyl ether, diglycerol tetraglycidyl ether, polyglycerol polyglycidyl ether, 2,6-sibricidyl phenylglycidyl ether, 2. 6. 2', 6-tetramethyl-4,4°-biphenyl glycidyl ether, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol S
glycidyl ether type epoxy compounds such as type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin and brominated epoxy resin, alicyclic gepoxy acetal, alicyclic gepoxy adibate and cycloaliphatic epoxy compounds such as vinylsixahexenedio, glycidyl (
Unsaturated acid glycidyl esters such as meth)acrylate, tetrahydroxyphthalic acid diglycidyl ester, sorbic acid glycidyl ester, oleic acid glycidyl ester, lyluic acid glycidyl ester, butyl glycidyl ester, octyl glycidyl ester, hexahydrophthalic acid diglycidyl ester Glycidyl ester-type epoxy compounds such as furkylcarboxylic acid glycidyl esters such as benzoic acid glycidyl ester, aromatic carboxylic acid glycidyl esters such as benzoic acid glycidyl ester, 0-phthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, and dimer acid glycidyl ester. , tetraglycidyldiaminodiphenylmethane, triglycidyl-p-7minophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-xylylenediamine, diglycidyltribromoaniline and tetraglycidylbisamino Examples include glycidylamine type epoxy compounds such as methylcyclohexane, heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidyl isocyanurate. Particularly preferred are glycidyl ether type epoxy compounds such as phenol novolak type epoxy resin, cresol novolac type epoxy resin, and halogenated phenol novolac type epoxy resin; 2. 6. 2゜6
Examples include heterocyclic epoxy compounds such as °-tetramethyl-4,4'-biphenylglycidyl ether and triglycidyl isocyanurate.

These epoxy compounds may be used alone or in combination of two or more, and the solid content of the photocurable resin composition is 100%.
5 to 40 parts by weight, preferably 10 to 30 parts by weight
Parts by weight can be used.

Examples of epoxy heat curing accelerators, which are heat curing catalysts for thermally reacting epoxy groups, include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropyltriamine), bis(hexamethylene)triamine, and 1,3 .6-1 Polyamines such as risaminomethylhexane, polymethylene diamines such as trimethylhexamethylene diamine, polyether diamine and diethylaminopropylamine, menthene diamine, isophone diamine, bis(4
-7 minnow 3-methylcyclohexyl)methane and N
-7 Aliphatic primary amines such as alicyclic polyamines such as minoethylbiperazine, aromatic primary amines such as metaphenylenediamine, diaminophenylmethane, diaminophenyl sulfone, and aromatic diamine eutectic mixtures, polyamines Epoxy resin adducts, poly7min-ethylene oxide 7 ducts, poly 7min-ethylene oxide 7 ducts, modified amines such as cyanoethylated polyamines and ketoimines, tertiary amines such as piperidine, piperazine, morpholine, and tetramethylguanidine, triethanolamine, Amine compounds such as tertiary amines such as hensyldimethylamine, 2,4.6-tris(dimethylaminomethyl)phenol, phthalic anhydride, trimellitic anhydride, ethylene glycol bis(anhydrotrimellitate) ), glycerin tris (an and dolotrimellitate), pyromellitic anhydride and 3.3', 4,4
° - Aromatic acid anhydrides such as benzophenone tetracarboxylic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,
Cyclic aliphatic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahyto-Ophthalic anhydride and methylcyclohexenetetracarboxylic anhydride, polyadipic anhydride aliphatic acid anhydrides such as polyazelaic anhydride and polysebacic anhydride, acid anhydrides such as halogenated acid anhydrides such as chlorendic anhydride and tetrabromophthalic anhydride, 2-methylimidazole, 2- Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole,
2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[ 2-
Methylimidazolyl-(1)]-]ethyl-s-triazine2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-]ethyl-5-1 riazine 2
．． 4-diamino-6-[2-undecylimidazolyl-
(1))-ethyl-5-triazine, 2-phenyl-4
-Methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroquinemethylimidazole, 1
-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-hensylimidazolium chloride and 1
．． Imidazole compounds such as 3-dibenzyl-2-methylimidazolium riOride, dicyandiamide, 0-
Trilbiguanide, phenylbeargeanide, and alpha-2
, dicyandiamide derivatives such as 5-dimethylbiguanide, carboxylic acids, phenols, quaternary ammonium salts, melamine derivatives, organic acid hydrazides, or methylol group-containing compounds. Particularly preferably dicyandiamide, 1-
Benzyl-2-methylimidazole is mentioned.

These epoxy thermosetting accelerators may be used alone or in combination of two or more.

Examples of organic solvents include ketones such as methyl ethyl ketone and hexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, calpitols such as calpitol and butyl cavitol, ethyl acetate, butyl acetate, cellosolve acetate,
Examples include acetic acid esters such as butyl cellosolve acetate, carpitol acetate, and butyl carpitol acetate.

These organic solvents may be used alone or in combination of two or more.

Furthermore, if necessary, the photocurable composition of the present invention may include a thermal polymerization inhibitor, a tackifier, an adhesion promoter, a dispersant, a plasticizer,
Auxiliary additives such as anti-sag agents, leveling agents, antifoaming agents, flame retardants, brighteners, colorants, etc. may be added.

Examples of thermal polymerization inhibitors include hydroquinone, p-
Methoxyphenol, pt-butylcatefur, 2.
Aromatic hydroxy compounds such as 6-di-t-butyl-p-cresol, β-naphthol, and pyrogallol, quinones such as benzoquinone and p-tol-beef non, naphthylamine,
Examples include amine necks such as pyridine, p-toluidine, and phenothiazine, aluminum salts or ammonium salts of N-nitrosophenylhydroxylamine, floranil, and nitrobenzene.

Examples of tackifiers or adhesion promoters include alkylphenol/formaldehyde novolac resins, borovinyl ethyl ether, polyvinyl isobutyl ether,
Polyvinyl butyral, polyisobutylene, styrene
Butadiene copolymer comb, butyl rubber, hinyl chloride-hinyl acetate copolymer, chlorinated rubber, acrylic resin adhesive,
Examples include aromatic, aliphatic or ring petroleum resins, silane coupling agents and the like.

As the silane coupling agent, known ones can be used, but KA1003, available from Borkoshi Silicone Co., Ltd.
, KBE1003. 8M1003, KBC4003,
KBM503, KBM303, KBM403, KBM8
03. KBE903゜KBM603. KBM703. 8E402. KBM602. KBM573 and A-175, A-188 available from Union Carbide,
A-1160 and the like can be preferably used. Particularly preferably KBM403. It is KBM303.

As the dispersant, for example, a fluorine-containing polymer compound, a surfactant such as a silicone surfactant, a modified lecithin, a non-silicon long chain carboxylic acid amine salt, an organic montmorillite, etc. are used.

Examples of plasticizers include glycol esters such as ethylene glycol siphthalate, diethylene glycol siphthalate, ethylene glycol capriate, and diethylene glycol dicabrate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diallyl phthalate, and butyl benzyl. Phthalic acid esters such as phthalate, phosphoric acid esters such as triphenyl phosphate and tricresyl phosphate, diethyl maleate, dibutyl adipate, triethyl citrate, and ethyl laurate are used.

Examples of flame retardants include inorganic flame retardants such as antimony trioxide, zirconium hydroxide, barium metaborate, magnesium hydroxide, and aluminum hydroxide, tetrabromobisphenol A, chlorinated paraffin, and perchloropentacyclo. Halogen-based flame retardant agents such as decane, tetrabromobenzene, and chlorinated diphenyl; and phosphorus agents such as vinyl phosphonate, allyl phosphonate, tris(β-chloroethyl) phosphonate, tricresyl phosphonate, and ammonium phosphate. flame retardants are used.

Further, inorganic fine powders such as talc, mica, silica, titanium dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, etc. may be added to the photopolymerizable composition of the present invention.

Further, other colorants may be contained as necessary.

Specific examples of coloring agents include inorganic pigments such as titanium oxide, carbon black, and iron oxide, organic dyes such as methylene blue, crystal violet, rhodamine B, tsuksin, auramine, azo dyes, and anthraquinone dyes, and phthalocyanine blue and phthalocyanine green. Phthalocyanine or azo organic pigments are used.

When forming permanent protective masks such as color filter layers, protective films for electronic devices, and solder resists for manufacturing printed wiring boards using the photocurable resin composition of the present invention obtained in this way, this composition After applying the substance to the substrate,
The coating film is dried by heating at a relatively low temperature to adjust the surface tackiness, and then pattern exposure is performed on the resulting coating film using a pattern mask. At this time, by heating and curing the coating film to eliminate the tackiness on the coating film surface before irradiating with actinic light, it is also possible to expose the cured coating film with a pattern mask in close contact with it. The film is then developed with an alkaline aqueous solution to elute the uncured film and obtain an image.

The photocurable resin composition of the present invention can be developed with an alkaline aqueous solution. As the developer, for example, an aqueous solution of 0.1 to 10% by weight of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, ammonia, etc. can be used.
In some cases, amines such as primary amines such as butylamine, hexylamine, benzylamine, allylamine, secondary amines such as diethylamine, benzylethylamine, tertiary amines such as triethylamine, ethanolamine, jetanolamine, triethanolamine, etc. ,
Hydroxylamines such as 2-amino-1,3-butopanediol, cyclic amines such as morpholine, pyridine, piperazine, piperidine, hydrazine, ethylenediamine,
Polyamines such as hexamethylene diamine, basic salts of the above amines such as sulfates, carbonates, bicarbonates, alkali metal phosphates, birophosphates, tetramethylammonium hydroxide, quaternary ammonium salts such as choline hydroxide etc. can also be used.

Methods for applying the photocurable resin composition of the present invention onto a substrate include, for example, a spin neat method, a spray method, a dip method, a brush coating method, a roller coating method, a flow coater method, a curtain coating method, and a screen printing method. In particular, for coating printed wiring boards, thin film metals, etc., spin cord methods, roller coating methods, curtain coating methods, screen printing methods, dispenser coating methods, etc. are preferred.

The photocurable resin composition of the present invention can be cured using both heat and light, and in particular, the photocurable resin composition of the present invention containing an organic solvent is used as a photocurable coating at low temperatures. Sometimes, the coating film is dried by heating to reduce the tackiness of the coating film surface before being irradiated with light. The heat curing conditions at this time are, for example, 60° C. to 120° C. for 5 minutes to 40 minutes. If it is less than this, it will be extremely sticky, and if it is more than this, there is a risk of deteriorating the devices to be bonded on the substrate. As a result of heating and curing in this manner, the tackiness can be adjusted to an appropriate level.

Moreover, the photocurable resin composition of the present invention can also be made into a cured film with improved heat resistance and moisture resistance by post-curing by heat treatment as necessary after light irradiation. The conditions at this time are preferably, for example, 120° C. to 200° C. and 10 minutes to 80 minutes.

If it is less than this, curing will be insufficient, and if it is more than this, there is a risk of deteriorating devices, substrates, etc.

Also, when forming a protective film for a color filter layer, 22
Sufficient cured film performance can be obtained by treatment at 0° C. to 250° C. for 30 minutes to 90 minutes.

For the heat treatment in curing before exposure and post-curing after image formation, a heating device such as a hot air circulation drying oven or a far-infrared drying oven can be used.

The exposure light source used for photocuring the photocurable resin composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp,
Ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, laser beams, etc. are included, but from 300 nm to
It is preferable to use an exposure apparatus whose light source is a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp that emits ultraviolet light around 400 nm.

EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. Note that unless otherwise specified, "parts" represent "parts by weight."

(Examples and Comparative Examples) Synthesis of Photopolymerizable Compound Epoxy compound (50 parts) shown in Table 1, unsaturated monocarboxylic acid (X part) in amount shown in Table 1, benzyltriethylammonium chloride (epoxy 1 for the group
mol%), 700p of nohydroquinone ((50+X)
pm) was dissolved in carpitol acetate in the amount shown in Table 1, and stirred at 80°C for 12 hours.

Tetrahydrophthalic anhydride in the amount shown in Table 1 was added to this reaction product, and the mixture was further stirred at 80°C for 2.5 hours to obtain photopolymerizable compound solutions Nos. 051 to 6.

Examples 1 to 3 and Comparative Examples 1 to 3 Preparation of coating liquid Using the photopolymerizable compounds 1 to 6 shown in the synthesis examples, one set of component M containing the photopolymerizable compound, composition amount 6 compositions, and an epoxy compound were prepared according to the following recipe. The component N1 composition containing the following was prepared by separately mixing and dissolving each component.

<Components M1 to M6> Photopolymerizable compound solution (70% solids concentration solution of compounds Nos. 1 to 6 in Table 1) 35 parts 2.6-Gt
-Butyl-p-cresol 0.05 parts Hensiphenone 0.7 parts 4.4"
-His(diethylamino) Hensiphenone 0.07 parts Tribromomethylphenylsulfone 03 parts Cellosolve acetate 25 parts Component M total composition 61.12 parts Component Nl> Phenol novolak type epoxy resin 28 parts (Epiclon N manufactured by Inu Nippon Ink Co., Ltd.) -695) Dipentaerythritol hexaacrylate 25.6 parts KBM40
3 (silane coupling agent 040 parts cellosolve acetate 40 parts component N1
Total composition: 97.6 parts Next, each of the obtained components M1 to M6 and N1 were mixed in a ratio of 4=1,
Photocurable resin composition (Examples 1 to 3 and Comparative Examples 1 to 3
) was obtained.

Performance Evaluation The performance of these photocurable resin compositions was evaluated by the following method, and the results are shown in Table 2.

1. Formation of coating film Photo-curing prepared under various conditions on a soda glass plate pretreated by removing moisture after performing alkaline cleaning, acid cleaning, and 2-propertool cleaning while irradiating ultrasonic waves. A synthetic resin composition is applied over the entire surface using a spin code method.
A coating film was obtained by drying at 80°C for 5 minutes in a hot air circulation type drying oven. (Thickness, 2 μm ± 0.2 μm) This coating film was irradiated with ultraviolet rays at 10,100 O/cm2 under an ultra-high pressure mercury lamp, developed for 1 minute with a weakly alkaline aqueous solution, and then developed at 180°C.
A cured film was obtained by post-heating for 60 minutes in a hot air circulation type drying oven.

2. Evaluation of sensitivity and developability ■ Step wedge (Fuji Photo Film Co., Ltd.)
After irradiating with ultraviolet rays at 10,100 O/cm 2 through a Δ0D=1.5), the film was developed with a weakly alkaline aqueous solution for 1 minute, and the sensitivity was evaluated based on the number of stages of the remaining film. (The higher the number of stages, the higher the sensitivity.) The developability was also evaluated based on the presence or absence of a film remaining in the unexposed area after development.

3. Evaluation of tackiness The coating film obtained by pretreatment, coating, and drying in the same manner as in 1 was evaluated for surface stickiness by a finger touch test.

4. Adhesion evaluation Regarding the cured film obtained in 1. JIS K 5400
6-15, the adhesion was evaluated by the base grain test method.

Example 4 and Comparative Examples 4 to 5 Using the photopolymerizable compounds 5.2 and 6 shown in the synthesis example, component M7 containing the photopolymerizable compound composition amount 9 composition and component N2 containing the epoxy compound were prepared according to the following recipe. Created a composition.

<Components M7 to M9> 350 parts of photopolymerizable compound solution (70% solids concentration solution of compounds Nos. 5.2 and 6 in Table 1) Florene rAC
-300J 15 parts (antifoaming agent manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) Phthalocyanine Green 2.
5 parts Irgacure 907 27.5 parts (Photo 1 initiator manufactured by Ciba Geigy) Silica 5 parts Barium sulfate 90 parts 1 to benzyl-2-methylimidazole 10 parts 500 parts Component M Total composition <Component N2> Triglycidyl isocyanurate Dipentaerythritol Hexaacrylate Talc 100 parts 36 parts 14 parts Cellosolve acetate 50 parts Component N2 Total composition 200 parts The above components M7 to 9 and component N2 were kneaded separately using a roll mill to prepare an ink.

Next, each of components M7 to M9 and component N2 were kneaded to form a photocurable resin composition (Example 4 and Comparative Examples 4 to 5).
I got it.

Table 3 shows the results of evaluating the performance of these photocurable resin compositions by the following method.

1. Formation of coating film The copper-clad laminate was pretreated by polishing, washing, and removing moisture. A photosensitive resin composition adjusted to suit each skin condition was applied to the entire surface of a pretreated copper-clad tank board by screen printing, and dried at 70°C for 30 minutes in a hot air circulation drying oven to obtain a coating film. .

2. Evaluation of developability The coating film was developed under the following conditions, and the time for the coating film to dissolve was measured.

Developer: 1% sodium carbonate aqueous solution Temperature:
・・25℃ Spray pressure□・・1.8Kg/cm'3. Sensitivity evaluation step wedge (manufactured by Fuji Photo Film Co., Ltd. △0D=
1.5) was adhered to the paint film and heated with a 5KW ultra-high pressure mercury lamp for 10 minutes.
00mj/cm21! 1. The time it takes for the paint film to dissolve when exposed to light.
Developed for 5 times as long to obtain a negative image corresponding to the wedge,
The number of stages at which the image was completely eluted (clear stage number) was determined.

A larger number indicates higher sensitivity.

4. Evaluation of tackiness The coating film obtained by pretreatment, coating, and drying in the same manner as in 1 was evaluated for surface stickiness by a finger touch test.

5. Evaluation of adhesion: After solid exposure with an exposure amount that gives a clear number of steps of 12, and after developing in the same manner as in 3, 5.
Post-cure for 0 minutes, JIS K 5400 6-15
A basic test was conducted in accordance with .

6. Insulation resistance evaluation The same method as the adhesion evaluation method was used except that a double-sided copper-clad laminate with a PC-B-25 test pattern was used.
After developing and post-curing, D
C500V was applied, and the resistance value was checked after 1 minute.

7. Evaluation of solder heat resistance In the same manner as the adhesion evaluation method, exposure, development, and post-curing were performed, and the temperature was 10% in a 260°C solder bath according to JISC6484.
The blistering and adhesion of the coating film after 5 cycles of solder float were comprehensively evaluated, with 1 second float being considered as one cycle.

(Effects of the Invention) The photocurable resin composition of the present invention is highly sensitive to ultraviolet light exposure, provides a coating film with low tackiness, has excellent developability in an alkaline aqueous solution, and has excellent heat resistance and substrate resistance of the cured film. It has excellent adhesion and electrical properties, making it ideal for applications such as color filter layers, protective films for electronic devices, and permanent protective masks for solder resists used in printed wiring board manufacturing.

Claims (1)

[Claims] (A) Photopolymerization obtained by sequentially reacting (1) a polyglycidyl ether compound obtained from a bisphenol S derivative, (2) an unsaturated monocarboxylic acid, and (3) a polybasic acid anhydride. 1. A photocurable resin composition comprising: (B) a radical photopolymerization initiator.