JPH0451242A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the compsn. which has a high sensitivity with UV exposing, forms a less tacky coated film, can be developed with an aq. alkaline soln. and has the excellent chemical resistance and chemical resistance of a cured film and the adhesive property thereof to a substrate by incorporating a photopolymerizable compd. and a photo radical polymn. initiator into the compsn. CONSTITUTION:Color filter layers, protective films for electronic devices, permanent protective masks, etc., are formed of the photosetting resin compsn. contg. the photopolymerizable compd. obtd. by successively bringing the epoxy compd. expressed by formula [where Ar denotes phenylene or substd. phenylene], unsatd. monocarboxylic acid and polybasic anhydride into reaction and the photo radical polymn. initiator. After this compsn. is applied on the substrate, the substrate is heated at a relatively low temp., by which the coating is dried and the tackiness of the surface is adjusted. This film is subjected to pattern exposing. The film is then developed by the aq. alkaline soln. to elute the uncured film and to obtain images. The film is subjected to post curing by a heating treatment at need after photoirradiation, by which the heat resistance and moisture resistance are improved.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photocurable resin composition, and more specifically,
A coating film with high sensitivity to ultraviolet exposure and low tackiness can be obtained, and it can be developed with an alkaline aqueous solution.The cured film has excellent chemical resistance, heat resistance, and adhesion to substrates, and is suitable for color filter layers and electronic 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 form of solder resist is dry film type or liquid resin N, i.
There are two types of products, but the latter is 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.

In addition, for other uses, with the development of color liquid crystal panels, there is an increasing demand for protective films for color filters. The main purpose of the protective film on the color filter is to improve the accuracy of the thickness of the liquid crystal layer and to flatten the surface above the color filter layer to prevent disconnections when installing the transparent electrode. It is necessary to have heat resistance against high-temperature treatment to lower the resistance. 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 harden when exposed to light,
It does not require heating or is easily cured by heating at relatively low temperatures, so processing time can be shortened.
Further, it is particularly suitable because it can prevent deterioration of the color filter layer 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. It is described that the protective film used in this case is coated with photocurable polyvinyl alcohol or the like. 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 in view of problems such as work 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 polyvinyl 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 problems, we
No. 253729 and No. 2-435i51 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 novolak type epoxy compound is used as bisphenol A diglycidyl ethyl or naphthalene diglycidyl ether, and these are combined with (meth)acrylic acid and polybasic acid. Although the use of photopolymerizable compounds obtained by sequentially reacting anhydrides has been described, no particular improvement in sensitivity has been observed with these.

(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, can be developed with an alkaline aqueous solution, and has good chemical resistance of the cured film. An object of the present invention is to provide a photocurable resin composition that has excellent heat resistance and adhesion to a substrate.

(Means for Solving the Problems) The object of the present invention is to: (A)[1] Sequentially prepare an epoxy compound represented by the following general formula (I), ■unsaturated monocarboxylic acid, and ■polybasic acid anhydride. The photopolymerizable compound obtained by the reaction has the general formula (I) [wherein, Ar represents phenylene or substituted phenylene]. ] and (B) a photo-radical polymerization initiator.

Typical epoxy compounds represented by general formula (I) include phenylene as Ar, or phenylene substituted with an alkyl group such as methyl group, ethyl group, propyl group, butyl group, or chloro group, bromo group, etc. phenylene substituted with a halogen group. These can be prepared by hand using a commercially available product such as Epicoat 1031S (manufactured by Yuka Shell Epoxy ■).

As the unsaturated monocarboxylic acid, compounds represented by the following general formula (■) are preferred.

General formula (n) CH2=CR1-Coo-R2-COOH 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 R2 include alkylene, substituted alkylene, phenylene, substituted phenylene, aralkylene/substituted aralkylene, those containing esters, ethers, ketones, thioethers, etc., or combinations thereof. Specifically, (meta)
Ring-opening reaction products of dimeric and trimeric oligomers (meth)acrylic acid and cyclic esters such as caprolactone by Michael addition of acrylic acid, (meth)acrylic acid hydroxyalkyl ester, trimethylolbroban di(meth) ) Acrylate, monoesterification reaction product of (meth)acrylate having a hydroxy group such as pentaeryswattol tri(meth)acrylate, glycerin di(meth)acrylate and dibasic acid anhydride, having the above hydroxy group Preferred examples include reaction products of (meth)acrylate and halogen-containing carboxylic acid compounds.

Among these, commercially available products that can be handled manually include Aronix M-5300 manufactured by Toagosei Chemical Industry Co., Ltd.
M-5400, M-5500 and M-5600, NK ester CB-1 and CB of Shin Nakamura Chemical Industry Co., Ltd. U
X-1, Kyoeisha Yushi Kagaku Kogyo Co., Ltd. I! HOA-MP
and HOA-MS, Viscoat #2100 manufactured by Osaka Organic Chemical Industry Co., Ltd., etc. can be used. Particularly preferably Aronix M-54 manufactured by Toagosei Chemical Industry Co., Ltd.
00 and 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.

Unsaturated monocarboxylic acid represented by general formula (n) and α, β
- An 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 (■) and the α,β-unsaturated monocarboxylic acid are used at the same time, The unsaturated monocarboxylic acid represented by the general formula (n) is first,
Or it may be later. In this case, the molar ratio of the unsaturated monocarboxylic acid represented by the general formula (n) to the α,β-unsaturated monocarboxylic acid is 100:O to 10:90, preferably 1
00:0 to 20:80. When the molar ratio of α,β-unsaturated monocarboxylic acid exceeds 90, sensitivity tends to decrease.

Typical polybasic @@hydrates include succinic anhydride, methylsuccinic anhydride, 2,3-dimethylsuccinic acid collection, 2,2-dimethylsuccinic anhydride, and dimethylsuccinic anhydride. substance, dodecenylsuccinic 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, tetrachloro Phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride,
Dibasic acid anhydrides such as chlorendic anhydride and 5-(2,5-dioxotetrahydrofuryl)-3-cyclohexene-1°2-dicarboxylic anhydride, glutaric anhydride, trimellitic anhydride, Polybasic acid anhydrides such as 3°3',4,4'-henzophenone tetracarboxylic anhydride can be used, but particularly preferred are tetrahydrophthalic anhydride, succinic anhydride, and maleic anhydride. can be mentioned.

The photopolymerizable compound of the present invention is obtained by sequentially reacting the above three types of compounds, and the ratio in which they are reacted is as follows: - an unsaturated monocarboxylic acid represented by drinking price (II), a mixture of the unsaturated monocarboxylic acid and (meth)acrylic acid, or (meth)acrylic acid, itaconic acid,
The carboxyl group such as cinnamic acid is 0.5 to 1.2 equivalents, preferably 0.8 to 1.1 equivalents, and the polybasic acid anhydride is 0.1 to 1.1 equivalents, preferably 0.5 to 1.2 equivalents. It is 3 to 1°0 equivalent. If the ratio of carboxyl groups is less than 0.5 equivalents, the sensitivity will decrease and the resin will become gelled, while if it exceeds 1.2 equivalents, a problem of tackiness will occur.

In addition, if the amount of polybasic acid anhydride is less than 0.1 equivalent, the developability will decrease, and 1. If the amount exceeds 1 equivalent, problems such as stickiness and crystal precipitation will occur.

These photopolymerizable 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 polymerization initiator used in the present invention include α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ether necks such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, thioxanthone, 2,
Thioxanthone such as 4-diethylthioxanthone, thioxanthone-1-sulfonic acid, thioxanthone-4-sulfonic acid, benzophenone such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone class, acetophenone, p-dimethylaminoacetophenone, α, α
'-dimethoxyacetoxyacetophenone, 2,2'-
Dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-[4-(methylthio)
Acetophenone neck and anthraquinone such as phenyl-2-morpholino-1-propanone, quinones such as 1゜4-naphthoquinone, phenansyl chloride, tribromomethylphenylsulfone, tris(trichloromethyl)-S-triazine, 2.4 Examples include -bis(trichloromethyl)-6-(4-methoxyphenyl)triazine, halogen compounds such as the compound described in JP-A-63-153542, and peroxides such as di-t-butyl peroxide. Particularly preferably 2,2'-dimethoxy-2
-Phenylacetophenone, 2-methyl-[4-(methylthio)phenyl-2-morpholino-1-propanone (trade name: Niirgacure 907, manufactured by Ciba Geigy)
).

These photoradical polymerization initiators may be used alone or in combination of two or more. Examples of mixing two or more types in this way include 2. 4. Combination of 5-triarylimidazole dimer and 2-mercaptobenzoxazole or leuco crystal violet, etc., US Patent No. 34
27161, a combination of 4,4'-bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether, US Pat. No. 4,239,850
The combination of benzoyl-N-methylnaphthothiazoline and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)triazine described in JP-A-1989-1999-
Combination of dimethylthioxanthone and 4-dialkylaminobenzoic acid ester described in No. 23602, 4,4'-bis(dialkylamino)benzophenone, ketones, and trihalogenated methyl-containing compound described in JP-A-59-78339 For example, a combination with

The total amount of these photoradical polymerization initiators is 0.0% relative to the photopolymerizable compound. 1 to 30 parts by weight is preferred, especially 0
．． Preferably, 15 to 15 parts by weight are used. 0. 1
If it is less than 30 parts by weight, the sensitivity will decrease, and if it exceeds 30 parts by weight, precipitation of crystals, insufficient hardening of the lower part, etc. will occur.

The photocurable resin composition of the present invention comprises the above-mentioned photopolymerizable compound,
In addition to the radical photopolymerization 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 monomethyl ether, 2-hydroxy-3-chloropropane, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, glycidol, 2-trimethoxysilylethanol, ethylene chlorohydrin, ethylene bromohydrin, 2,3 -Dibromopropanol, allyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol, naphthol and the like. In addition, as a polyhydric alcohol,
For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, dodecanediol, neopentyl glycol , 1°10-
Decanediol, 2-butene-1,4-diol, 2-
n-butyl-2-ethylpropanediol, cyclohebutanediol, 1,4-cyclohexane dimetatool,
3-cyclohexene-1,1-jetanol, polyethylene glycol (diethylene glycol, triethylene glycol, etc.), polypropylene glycol (dipropylene glycol, tribucobylene 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. 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, pyrogallol, α-(I-aminoethyl)-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)-jetanolamine, 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-(l-
aminoethyl)-p-hydroxybenzyl alcohol,
Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, α-mannitol, butanetriol, 1. 2
．． 6-1 hydroxyhexane, 1, 2. Examples include 4-benzenetriol, triethanolamine, 2,2-bis(hydroxymethyl)-2,2',2''-nitrilotriethanol, etc. Esters of (meth)acrylic acid of these monohydric or polyhydric alcohols Of these, 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, ) acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)
Acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, sorbitol hexa(meth)acrylate, sorbitol penta(meth)acrylate, etc. are preferred, and dipentaerythritol hexa(meth)acrylate is particularly preferred. Can be mentioned.

In addition, monoamine or polyamine (meth)acrylamide can also be used. Examples of monoamines include monoalkylamines such as ethylamine, butylamine, amylamine, hexylamine, octylamine, cyclohexylamine, and 9-aminodecalin; 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-aminopropyl)amine, diethylenetriamine, triethylenetetraamine, polyethylenepolyamine, tris(2-aminoethyl)amine, 4°4'-methylenebis(cyclohexylamine),
N,N'-bis(2-aminoethyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)-1,4-butanediamine, N,N'-bis(3
-aminopropyl)ethylenediamine, N,N'-bis(3-aminopropyl)-1,3-propanediamine,
1.3-Cyclohexanebis(methylamine), phenylenediamine, xylylenediamine, β-(4-aminophenyl)ethylamine, diaminotoluene, diaminoanthracene, diaminonaphthalene, diaminostyrene, methylenedianiline, 2,4-bis( Examples include 4-aminobenzyl)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. may 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, divinyl 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 Aronix M5700 and M6 manufactured by Toagosei Chemical Industry Co., Ltd.
100. M8O30, M152, M2O3, M215,
Acrylate monomers such as M315 and M325 NK ester 2C;, 4G, 9C; manufactured by Shin-Nakamura Chemical Co., Ltd.
14G, ABPE-4, A-TMPTS U-4HAS
CB-1, CBX-1, KAYARAD manufactured by Nippon Kayaku Co., Ltd.
R604, DPCA-30, DPCA-60, KA
(Meth)acrylate monomers such as YAMARPM-1, PM-2, Photomer 4061.5007 manufactured by San Nobuco Co., Ltd. Lipoxy VR60, VR90 manufactured by Showa Kobunshi Co., Ltd.
Epoxy acrylates such as SP 1509, spirane resins having a spiroacetal structure and a (meth)acrylic group such as Subilac E-4000X and U3000 manufactured by the same company, etc. 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
type epoxy resins, phenol novolak type epoxy resins, cresol novolac type epoxy resins, halogenated phenol novolac type epoxy resins, glycidyl ether type epoxy compounds such as brominated epoxy resins, alicyclic gepoxy acetals, alicyclic gepoxy adipates, and Cycloaliphatic epoxy compounds such as vinyl cyclohexene dioxide, 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 alkyl carboxylic acid glycidyl esters and 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-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-xylylenediamine, diglycidyltribromoaniline and tetraglycidylbisaminomethylcyclohexane Examples include glycidylamine type epoxy compounds such as, diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and heterocyclic epoxy compounds such as triglycidyl isocyanurate. Particularly preferably, 2. 6. 2', 6
Heterocyclic epoxy compounds such as '-tetramethyl-4゜41-biphenylglycidyl ether and triglycidyl isocyanurate are exemplified.

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-) Polyamines such as risaminomethylhexane, polymethylene diamines such as trimethylhexamethylene diamine, polyether diamine and diethylaminoprobylamine, menthene diamine, isophorone diamine, bis(4-amino-3-methyl aliphatic primary amines such as alicyclic polyamines such as cyclohexyl)methane and N-aminoethylpiperazine; aromatic primary amines such as metaphenylenediamine, diaminophenylmethane, diaminophenyl sulfone and aromatic diamine eutectic mixtures; ,
Polyamine epoxy resin adducts, polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, modified amines such as cyanoethylated polyamines and ketoimines, tertiary amines such as piperidine, piperazine, morpholine, and tetramethylguanidine, triethanolamine, benzyldimethylamine, 2. 4
．． 6-) Amine compounds such as tertiary amines such as lis(dimethylaminomethyl)phenol, phthal W1 anhydride,
trimellitic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerin tris(anhydrotrimellitate), pyromellit vi anhydride and 3
．． 3', 4. Aromatic acid anhydrides such as 4'-benzophenone tetracarboxylic anhydride, maleic anhydride,
Amber R11 anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, alkenylsuccinic anhydride, boiled hexahydrophthalic acid, methyl Cyclic aliphatic acid anhydrides such as hexahydrophthalic anhydride and methylcyclohexenetetracarboxylic anhydride, aliphatic acid anhydrides such as polyadipic anhydride, polyazelaic anhydride and polysebacic anhydride, chlorendic acid anhydride and acid hydrides such as halogenated acid anhydrides such as tetrabromohydrophthalic acid, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-(I)
]-]Ethyl-5-riazine, 2,4-diamino-6-
[2-ethyl-4-methylimidazolyl-(I)]-]
Ethyl-5-riazine, 2,4-diamino-6-[2-
Undecylimidazolyl-(I)-ethyl-5-)riazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl- Imidazole compounds such as 4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride, dicyandiamide, 0 - Dicyandiamide compounds such as tolylbiguanide, phenylbiguanide, and α-2,5-dimethylbiguanide, carboxylic acids, phenols, quaternary ammonium salts, melamine derivatives, organic acid hydrazides, or methylol group-containing compounds, etc. Known epoxy curing accelerators may be mentioned. Particularly preferred are dicyandiamide and 1-benzyl-2-methylimidazole.

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 cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, carpitols such as calpitol and butyl cavitol, ethyl acetate, butyl acetate, and 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, an i-agent,
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-butylcatechol, 2,
Aromatic hydroxy compounds such as 6-di-t-butyl-p-cresol, β-naphthol and pyrogallol, quinone necks such as benzoquinone and p-torquinone, naphthylamine,
Examples include amines 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 rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chloride rubber, acrylic resin adhesive,
Examples include aromatic, aliphatic or alicyclic petroleum resins, silane coupling agents and the like.

Known silane coupling agents can be used, including KA1003 available from Shin-Etsu Silicone Co., Ltd.
, KBE1003. KBM1003, KBC1003,
KBM503, KBM303, KBM403, KBM8
03. KBE903゜KBM603. KBM703. K
BE402. KBM602. KBM573 and A-175, A-188 available from Union Carbide,
8-1160 etc. can be preferably used. Particularly preferably KBM403. It is KBM303.

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

Examples of the lubricant include glycol esters such as ethylene glycol siphthalate, diethylene glycol siphthalate, ethylene glycol capriate, diethylene glycol dicabrate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diallyl phthalate, butyl Phthalic acid esters such as benzyl 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 dioxide, zirconium hydroxide, barium metaborate, magnesium hydroxide, and aluminum hydroxide, tetrabromobisphenol A, chlorinated paraffin, and perchloropentacyclodecane. , tetrabromobenzene, chlorinated diphenyl, and other halogen-based flame retardants, and phosphorus-based flame retardants 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, silicon dioxide, titanium dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, 5RWIL magnesium, 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 colorants include inorganic pigments such as titanium oxide, carbon black, and iron oxide, organic dyes such as methylene blue, crystal violet, rhodamine B, tuxin, auramine, azo dyes, and anthraquinone dyes, and phthalocyanines such as phthalocyanine blue and phthalocyanine green. or azo-based 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 21 things to the board! After the cloth is coated, it is dried by heating at a relatively low temperature to adjust the surface tackiness, and then the resulting coating film is subjected to pattern exposure using a pattern mask. At this time, before irradiating the active light, the coating film is heated and cured to eliminate the tackiness on the coating film surface, making it possible to expose the pattern mask in close contact with the cured coating film using an alkaline aqueous solution. It is developed and the uncured film is dissolved to obtain an image.

The photocurable resin composition of the present invention can be developed with an alkaline aqueous solution. As the developer, for example, a 0.1 to 10% by weight aqueous solution 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-propanediol, 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 You can also use .

Methods for applying the photocurable resin composition of the present invention onto a substrate include, for example, a spin cord 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.

Further, the photocurable resin composition of the present invention can be post-cured by heat treatment, if necessary, after irradiation with light to form a cured film with improved heat resistance and moisture resistance. 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 is 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. may be used, but 300 nm to 4
It is preferable to use an exposure apparatus using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp as a light source that emits ultraviolet rays around 0 Onm.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples. In addition, unless otherwise specified, "1 part" represents "part by weight."

(Examples and Comparative Examples) Synthesis of Photopolymerizable Compound Epoxy resin (50 parts) shown in Table 1, unsaturated monocarboxylic acid (X part) in the amount shown in Table 1, benzyltriethylammonium chloride (epoxy 1 mol%), 700 ppm of hydroquinone ((50+X)
) 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 No. 1 to No. 5.

Examples 1 to 2 and Comparative Examples 1 to 3 Preparation of coating liquid Component M+ containing the above photopolymerizable compound according to the following formulation
A total of 5 compositions and a component N2H composition containing an epoxy resin were individually crushed and dissolved.

<Component Ml-MS> Photopolymerizable compound solution (70% solids concentration solution of compounds Nos. 1 to 5 in Table 1) 35 g 2.6-G-T-
Butyl-p-cresol 0.05g Hensiphenone 0.7g4.4
'-Bis(diethylamino) Benzophenone 0.07g Tribromomethylphenylsulfone 0.3g Cellosolve acetate 25g Component M total composition 61.12g <Component Nl> Phenol novolac type epoxy resin 28g (Dainippon Ink Co., Ltd. Epicron N-695) Di Pentaerythritol hexaacrylate 25.6gKBM40
3 (Silane coupling agent) 4.0g Cellosolve acetate 40g Component N1
Total composition: 97.6g Next, each of the obtained components Ml-M5 and Nl were mixed at a ratio of 4:1 to form a photocurable resin composition (Examples 1-2 and Comparative Examples 1-3).
) was obtained.

Performance Evaluation The performance of these photocurable resin compositions was evaluated by the following method.

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.
After heating for 60 minutes in a hot air circulation type drying oven, a cured film was obtained.

2. Evaluation of sensitivity and developability A step wedge (Fuji Photo Film) was applied on the coating film obtained by pretreatment, coating, and drying in the same manner as in 1.
After irradiating with ultraviolet rays at 10,100 O/cm2 via a ΔD=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. The results are shown in Table-2.

3. Tackiness evaluation 1. The coating film obtained by pretreatment, coating, and drying in the same manner as above was evaluated for surface tackiness by a finger touch test. The results are shown in Table-2.

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. The results are shown in Table-2.

(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, can be developed with an alkaline aqueous solution, and has good adhesion to the substrate of the cured film. Excellent for preserving color filter layers and electronic devices,
For applications such as permanent protective masks for solder resists used in printed circuit board manufacturing! suitable.

Claims (1)

[Scope of Claims] A photocurable resin composition characterized by containing the following (A) and (B). (A) [1] A photopolymerizable compound obtained by sequentially reacting an epoxy compound represented by the following general formula (I), [2] an unsaturated monocarboxylic acid, and [3] a polybasic acid anhydride, the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Ar represents phenylene or substituted phenylene. ] (B) Radical photopolymerization initiator.