JPH02190860A - Liquid photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide the resin compsn. which can be photoset and thermoset, provides high sensitivity, excellent electrical characteristics, mechanical characteristics, and chemical resistance and can be developed by an alkaline aq. soln. by incorporating a specific modified polystyrene resin, polymerizable compd., epoxy compd., photopolymn. initiator or photopolymn. initiator system, thermosetting catalyst which brings an epoxy group into thermal reaction, and org. solvent into the compsn. CONSTITUTION:This compsn. contains the modified polystyrene resin obtd. by successively bringing the high-molecular polymer having the repeating unit expressed by the formula I, the compd. having carboxyl group and ethylenic unsatd. double bonds in the molecule and satd. or unsatd. polybasic acid anhydride into reaction, the polymerizable compd. having at least one ethylenic unsatd. double bonds, the epoxy compd. having at least one epoxy group, the photopolymn. initiator or the photopolymn. initiator system, the thermosetting catalyst which brings the epoxy group into thermal reaction, and the org. solvent. In the formula 1, R denotes hydrogen or methyl group; Ar denotes phenylene or substd. phenylene. The resin compsn. which can be photoset and thermoset, provides the high sensitivity and the excellent electrical characteristics, mechanical characteristics and chemical resistance, and can be developed with the alkaline developing soln. is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a liquid photosensitive resin composition, and more particularly, to a liquid photosensitive resin composition that can be used to form a permanent protective mask such as a solder resist for manufacturing printed wiring boards. The present invention relates to a liquid photosensitive resin composition that is highly sensitive to ultraviolet light exposure, has excellent electrical properties and chemical resistance of a cured coating film, and is photocurable and thermocurable.

(Prior art) Conventionally, in the printed wiring board industry, resin compositions used for permanent protective masks such as solder resists and chemical plating resists are mainly composed of thermosetting resins such as epoxy resins and melamine resins. For pattern formation,
Screen printing methods have been widely used. The main purpose of solder resist is to limit the area during soldering, to prevent non-dub ridges, etc., to prevent corrosion of conductors, and to maintain electrical insulation between conductors over a long period of time. be.

However, in recent years, with the high-density packaging of VLSIs, etc., there has been a need to reduce the spacing between conductors, and there have also been strict requirements for electrical insulation between conductors, and solder resists with excellent dimensional accuracy are now required. However, screen printing methods inherently have low resolution and are prone to scratches, pinholes (in the case of high viscosity inks) or bleeds, smears,
Phenomena such as sagging (when the viscosity is low) occur, making it difficult to cope with the increasing density of printed wiring boards.

Therefore, the photographic method (forming an image by image exposure followed by development)
Photosensitive resin compositions that can form patterns with high sensitivity, high resolution, and excellent adhesion to substrates, as well as excellent electrical and mechanical properties of the coating film after curing, are currently attracting attention. There is.

Furthermore, in recent years, due to problems such as work environment, air and water pollution, photosensitive resin compositions that can be developed with alkaline aqueous solutions or water have been desired.

Developable photosensitive resin compositions in dry film type or liquid form have been developed as permanent protective masks for printed wiring boards whose patterns are formed by photography.

As a dry film type photosensitive resin composition, for example,
Urethane di(meth) in JP-A No. 57-55914 etc.
A photosensitive resin composition comprising an acrylate, a linear polymer compound, and a photosensitizer is also disclosed in JP-A-62-24735.
No. 3 discloses a photosensitive resin composition comprising a (meth)acrylic modified resin of a specific novolac epoxy resin and a photosensitizer.

However, in the case of dry film type photosensitive resin compositions for boat fishing, air bubbles are likely to occur during heat-pressing, and there are concerns about heat resistance and adhesion. As disclosed in Japanese Patent Application Laid-Open No. 52-52703, special processes such as heat-compression bonding under reduced pressure are required, and even if such processes are used, perfect heat resistance and adhesion cannot be obtained. Not guaranteed.

On the other hand, liquid developable photosensitive resin compositions require fewer steps because they are applied directly to printed wiring boards in liquid form immediately before use, and because they are liquid, they are also suitable for printed wiring boards with severe unevenness. It can form an excellent image and is suitable, for example, as a photosensitive resin composition for permanent protective masks for printed wiring boards with narrow conductor spacing.

However, this liquid photosensitive resin composition also has the disadvantage that, after being applied onto a printed wiring board, if the pattern mask is brought into direct contact with the coating surface and exposed to light, the pattern mask becomes dirty.

As a method for solving this pattern mask stain, as disclosed in JP-A-57-164595, etc., a conventional method involves coating a printed wiring board with a liquid photosensitive resin composition and then drying it to form a film. Unlike the above method, there is a special method in which patterned masks are placed at intervals in a liquid state without drying, exposed to light and cured, and the uncured liquid photosensitive resin composition is removed. However, because it does not form a dry film, it is necessary to leave a gap between the surface of the liquid photosensitive composition coated and the pattern mask, which reduces resolution, and requires special equipment, which is expensive. be.

Furthermore, in JP-A No. 58-24144.59-2049, etc., a liquid photosensitive resin composition is applied to a uniform thickness on a transparent flexible support or patterned mask that transmits actinic rays, and Immediately, move the flexible support or pattern mask and press the surface coated with the liquid photosensitive resin composition against the printed wiring board with a constant pressure to spread the liquid photosensitive resin composition uniformly on the printed wiring board. Laminated thickly, then exposed,
A method of manufacturing a solder resist by peeling off and developing a flexible support or patterned mask is disclosed. In this method, a liquid photosensitive resin composition is applied to a transparent flexible support or a patterned mask in a uniform thickness, and then when pressed with a constant pressure toward a printed wiring board, unevenness is created on the printed wiring board. Because of this, air bubbles may be trapped, causing considerable air bubbles to appear in the image, causing concerns about heat resistance and adhesion.
Furthermore, there are other problems such as the need for specific equipment, which is expensive.

Furthermore, JP-A-61-102652.62-27736
The publication discloses that after a liquid photosensitive composition is applied onto a printed wiring board, a transparent flexible support or a pattern mask is pressed with a constant pressure, light is misted through the pattern mask, and the flexible support is coated with a liquid photosensitive composition. A method of manufacturing a solder resist by peeling off a body or pattern mask and then developing it is disclosed.

These methods also have problems, such as the need for specific equipment for pressing the flexible support or patterned mask with a constant pressure and exposing the material, resulting in high costs.

Furthermore, in the method described above in which the liquid photosensitive composition is directly exposed to light according to the resist pattern without drying, the liquid photosensitive composition uses a liquid prepolymer containing a large number of reactive monomers, so the liquid photosensitive composition has acid resistance. There is also the problem that properties such as chemical resistance are inferior to conventional methods.

A method of forming a solder resist by applying a liquid photosensitive resin, heating and drying it, exposing it with a pattern mask, and developing it is described in Japanese Patent Application Laid-Open No. 61-2438.
A liquid resist ink composition containing a compound obtained by reacting a novolac-type epoxy compound, an unsaturated monocarboxylic acid, and a polybasic acid anhydride, as disclosed in JP-A No. 62-187722, etc. There is a liquid resin composition whose main component is a bisphenol-type epoxy resin having an unsaturated group and a carboxyl group.

However, these liquid photosensitive resin compositions also have insufficient sensitivity and properties such as electrical properties and chemical resistance of the coated film after curing.

(Point H to be solved by the invention) An object of the present invention is to solve the above-mentioned conventional technical problems and to be able to form a photosensitive resin layer of uniform thickness without bubbles on a printed wiring board. In addition, by heating a printed wiring board coated with a photosensitive resin before exposure, the adhesiveness of the photosensitive resin coating surface is eliminated, and the coating surface and pattern mask can be exposed in close contact with each other. To provide a liquid photosensitive resin composition that can be both cured and thermocured, has high sensitivity, provides a cured coating film with excellent electrical properties, mechanical properties, and chemical resistance, and can be developed with an alkaline aqueous solution. It is in.

(Means for Solving the Problems) The present inventors have discovered that the above problems can be solved by using the following liquid photosensitive resin composition,
This application has been filed.

(A) A polymer having a repeating unit of the following general formula (I), a compound having a carboxyl group and an ethylenically unsaturated double bond in the same molecule, and a saturated or unsaturated polybasic acid anhydride are sequentially reacted. The modified polystyrene resin obtained by general formula (I) means phenylene or substituted phenylene. ) (B) Polymerizable compound having at least one ethylenically unsaturated double bond (C) Epoxy compound having at least one epoxy group (D) Photoinitiator or photoinitiator system (E) Epoxy A liquid photosensitive resin composition containing a thermosetting catalyst (F) an organic solvent that causes a group to undergo a thermal reaction.

Each component of the liquid photosensitive resin composition of the present invention will be explained below.

The modified polystyrene resin (A) is a polymer having a repeating unit of general formula (I), a compound having an epoxy group and an ethylenically unsaturated double bond in the same molecule, and a saturated or unsaturated polybasic acid. Obtained by sequentially reacting anhydrides.

Examples of the polymer having the repeating unit of general formula (I) include 4-vinylphenylglycidyl ether, 4-isopropenylphenylglycidyl (wherein R is boron, or a methyl group, Δr ether, 2- Ethyl-4-vinylphenyl glycidyl ether, 2-isopropyl-4-
Vinylphenylglycidyl ether, 2.6-taituprobyl-4-vinylphenylglycidyl ether, 2.
6-di-t-butyl-4-vinylphenylglycidyl ether, 2,6-di-t-butyl-4-isopropenylphenylglycidyl ether, brominated-4-vinylphenylglycidyl ether, fluorinated 4-isopropenylphenylglycidyl ether Homovinyl polymers such as
Alternatively, examples include vinyl copolymers with vinyl monomers copolymerizable with these. In addition, these compounds include 4-vinylphenol, 4-impropenylphenol, 2-
Ethyl-4-vinylphenol, 2-isopropyl-4
-vinylphenol, 2.6-diisopropyl-4-vinylphenol, 2.6-di-t-butyl-4-vinylphenol, 2I5-'; -t-j thi-4-impropenylphenol, from-4-vinyl phenol,
It can be obtained by reacting a homopolymer such as brominated 4-impropenylphenol or a copolymer with a monomer copolymerizable with the same with epichlorohydrin in the presence of an alkali. Among these, particularly preferred examples include vinyl polymers of 4-vinylphenyl glycidyl ether and vinyl polymers of 4-isopropenylphenyl glycidyl ether.

Compounds having a carboxyl group and an ethylenically unsaturated double bond in the same molecule include acrylic acid, methacrylic acid, dimers, trimers or higher polymers of acrylic acid, acrylic acid or methacrylic acid, and caprolactone. Reaction products of hydroxyalkyl esters of acrylic acid or methacrylic acid and dibasic acid anhydrides, reaction products of hydroxyalkyl esters of acrylic acid or methacrylic acid and halogen-containing carboxylic acids products, vinylbenzoic acid, etc.

Furthermore, as commercially available products, γronix M-5300, M-5400, M-550 manufactured by Toagosei Chemical Industry Co., Ltd.
0 and M-5600, NK manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
Ester CB-1 and CBX-1, Kyoeisha Yushi Kagaku Kogyo Co., Ltd.! 8! HOΔ-qP and HOA-MS, Visco) #2100 manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be used.

Among these, particularly preferred specific examples include dimers, trimers, and higher polymers of acrylic acid, methacrylic acid, and acrylic acid.

In addition, examples of saturated or unsaturated polybasic acid anhydrides include succinic anhydride, methylsuccinic anhydride, 23-dimethylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, ethylsuccinic anhydride, dodecenylsuccinic anhydride, nonenylsuccinic anhydride, Maleic anhydride, methylmaleic anhydride, anhydride 2
．． 3-dimethylmalein M, anhydrous 2-chloromalein L
a water 2.3-dichloromaleic acid, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cis-acottic anhydride, phthalic anhydride, tetrahydrophthalic anhydride,
Tetrachlorophthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride and 5- Dibasic acid anhydrides such as (2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, 3.3
', 4.4°-benzophenonetetracarboxylic acid, and other polybasic acid anhydrides can be used. Among these, the dibasic acid anhydrides mentioned above are preferred, and succinic anhydride and tetrahydrophthalic anhydride are particularly preferred.

A modified polystyrene resin is obtained by reacting each of them in sequence, and the ratio of reacting them is such that the number of carboxyl groups in the same molecule per equivalent of epoxy group of the polymer having the repeating unit of general formula (I) is and 0.5 to 1.2 equivalents, preferably 0.8 to 1.1 equivalents of the compound having an ethylenically unsaturated double bond, and 0.1 equivalent of the polybasic acid anhydride.
~1°1 equivalent, preferably 0.3-1. It is 0 equivalent. If the amount of the compound having a carboxyl group and an ethylenically unsaturated double bond in the same molecule is less than 0.5 equivalent, the sensitivity will decrease, and if it exceeds 1.2 equivalent, a problem of stickiness will occur. Furthermore, if the amount of the polybasic acid anhydride is less than 0.1 equivalent, the developability will deteriorate and the resin will become gelled, while if it exceeds 1.1 equivalent, problems such as stickiness and crystal precipitation will occur.

These modified polystyrene resins may be used alone or in combination of two or more, and the solid content of the liquid photosensitive resin composition is 100 weight! It is preferably 10 to 60 parts by weight, particularly preferably 20 to 50 parts by weight. 10
If it is less than 60 parts by weight, the developability and strength of the cured film will be reduced, and if it exceeds 60 parts by weight, the liquid viscosity will be high and workability will be reduced.

Examples of the polymerizable compound having at least one ethylenically unsaturated double bond used in the present invention include esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohols.

Examples of monohydric alcohols in the esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohols include methanol, ethanol, propatool, imbrobanonopen n-butanol, imbutanol, t-butanol, cyclohexylalconohbenzyl. Alcohol, octyl alcohol, 2-ethylhexanol, lauryl alcohol, n-decanol, undecanol, heptyl alcohol, stearyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, butoxyethyl alcohol, polyethylene glycol monomethyl alcohol, polyethylene glycol monoethyl alcohol, 2 -Hydroxy-3-chloropropane, dimethylamino alcohol, diethylamino alcohol, glycidol, 2-trimethoxysilylethanol, ethylene chlorohydrin, ethylene bromohydrin, 2,3-sifurompropatur, allyl alcohol, oleyl alcohol, epoxystearyl Anolicol, phenol,
Examples include naphthol. Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, hexanediol, heptanediol, octanediol, and nonanediol. , dodecanediol, neopentyl glycol, 1.
10-decalidiolpe 2-butene-1,4-diol, 2 n-butyl-2-ethylpropanediol,
Cyclohebutanediol, I,4-cyclohexanedimethanol, 3-cyclohexene-1,1-jetanol, polyethylene glycol (diethylene glycol)
triethylene glycol, etc.), polypropylene glycol (dipropylene glycol, tripropylene glycol, etc.), polystyrene oxide glycone polytetrahydrofuran glycol, xylylene diol, bis(
β-hydroxyethoxy)benzene, 3-chloro-1,
2-propanediol, 2.2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanedionobe 2.2-diphenyl-1,3-propanediol, decalindiol, 1,5 -dihydroxy-1,
2,34-tetrahydronaphthalene, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-13-hexanediol, 2-ethyl-2-(hydroxymethyl)
-1,3-propanediol, 2-ethyl-2-methyl-1,3-7'lovandiol, 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゜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-furopanediol, 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-1,2-7'ropanediol,
3-piperidine-1,2-propanediol, 2-(2
-pyridyl)-1,3-propanediol, α-(I-
aminoethyl)-p-hydroxybenzyl alcohol,
Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, α-mannitol, butanetriol, 1.2.
Examples thereof include 6-trihydroxyhexane, 1,2,4-benzenetriol, triethanolamine, 2,2-bis(hydroxymethyl)-2,2',2''-nitrilotriethanol, etc. Among the esters of acrylic acid or methacrylic acid of alcohols,
Ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate,
Dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate , neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, sorbitol hexaacrylate, sorbitol hexamethacrylate, sorbitol pentaacrylate, sorbitol pentamethacrylate and the like are preferred.

It is also possible to use mono- or polyamine acrylamide or methacrylamide. Examples of monoamines include monoalkylamines such as ethylamine, butylamine, amylaminehexylamine, 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, methylene dianiline, 24-bis(4-
Examples include 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 polyallylic esters of mono- or polycarboxylic acids such as chlorendic acid and trimellitic acid, mono- or polyallylic esters of mono- or polysulfonic acids such as benzenedisulfonic acid, naphthalenedisulfonic acid, diallylamine, N,N'-diallylsiniuic 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-inpyrobenyl styrene, divinyl sulfone, ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl phthalate, divinyl phthalate, divinyl terephthalate, etc., 2
Acrylic acid or methacrylic acid ester compounds having an ionic group such as -hydroxy-3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyphenyltrimethylammonium 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, M8030, M152, M2O3, M215,
Acrylate monomers such as M315 and M325, NK ester ABPE-4 and U-4H manufactured by Shin-Nakamura Chemical Co., Ltd.
ASCB-1YAMΔRPM-1, PM-2, acrylate or methacrylate monomers such as Photomer 4061.5007 manufactured by San Nobuco, epoxy acrylates such as Lipoxy VR60, VR90, 5P15C19 manufactured by Showa Kobunshi Co., Ltd., Spirac E-4000X, U3 manufactured by Showa Kobunshi Co., Ltd.
A spirane resin having a spiroacecool structure such as 000 and an acrylic group or a methacrylic group can also be used.

These compounds may be used alone or in combination of two or more, and are preferably used in an amount of 1 to 40 parts by weight, particularly 2 to 30 parts by weight, based on 100 parts by weight of the solid content of the liquid photosensitive resin composition. It is preferable. If it is less than 1 part by weight, the sensitivity will decrease, and if it exceeds 40 parts by weight, the electrical properties and mechanical properties of the cured film will decrease.

Examples of the compound having at least one epoxy group used in the present invention include butyl glycidyl ether,
Glycidyl ethers of alcohols having 2 to 20 carbon atoms such as octyl glycidyl ether, decyl glycidyl ether, aryl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycidyl ether, etc. Glycidyl ether, neobentyl glycol sifuricidyl ether, 1゜6-hexanethiol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol tetraglycidyl ether novel polyglycerol Polyglycidyl ethers of polyols such as polyglycidyl ether, 2,6-siblycidyl phenylglycidyl ether, 2.62',6'-tetramethyl-4,4°-biphenyl diglycidyl ether, bisphenol A type epoxy resin, Hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin,
Glycidyl ether type epoxy compounds such as bisphenol S type epoxy resin, hydrogenated bisphenol S type epoxy resin, phenol novolak type epoxy resin, Talezol novolac type epoxy resin, halogenated phenol novolac type epoxy resin and brominated epoxy resin, Arisai Cycloaliphatic epoxy compounds such as Click Gepoxy Acecool, Alicyclic Gepoxy Adibate, Alicyclic Gepoxy Adipate and Vinyl Cyclohexene Dioxide, Glycidyl Acrylate, Glycidyl Methacrylate, Tetrahydroxyphthalic Acid Diglycidyl Ester, Sorbic Acid Unsaturated acid glycidyl esters such as glycidyl estenopeoleic acid glycidyl ester and lyluic acid glycidyl ester; alkyl carboxylic acid glycidyl esters such as butyl glycidyl ester, octyl glycidyl ester, hexahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester; and glycidyl ester type epoxy compounds such as aromatic carboxylic acid glycidyl esters such as benzoic acid glycidyl ester, 0-phthalic acid diglycidyl ester and diglycidyl p-oxybenzoic acid, tetraglycidyl diaminodiphenylmethane,
Glycidylamine types such as triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-xylylenediamine, diglycidyltribromoaniline and tetraglycidylbisaminomethylcyclohexane. Epoxy compounds, heterocyclic epoxy compounds such as diglycidyl hydantoin, glycidylglycidoxyalkylhydantoin, and triglycidyl isocyanurate can be mentioned. Among these, 2.
6.2°, 6′-tetramethyl-4,4° biphenyl diglycidyl ether, novolac type epoxy resin, and heterocyclic epoxy compound are preferred.

These epoxy compounds may be used alone or in a mixture of two or more, and preferably 1 to 40 parts by weight, particularly 5 to 3 parts by weight, based on 100 parts by weight of the solid content of the liquid photosensitive resin composition.
Preferably, 0 part by weight is used. If it is less than 1 part by weight, the strength, chemical resistance, and electrical properties of the cured film will be insufficient, and if it exceeds 40 parts by weight, the stability of the liquid will decrease.

Examples of the photopolymerization 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, 4,4°-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone Benzophenone neck, acetophenone, p-dimethylaminoacetophenone, α, α° etc.
-dimethoxyacetoxyacetophenone, 2,2° -
diftquin-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-(4-(methylthio)
Acetophenones such as phenyl-2-morpholino-1-propanone, quinones such as anthraquinone and 1,4-naphthoquinone, and halogens such as phenacyl chloride, trifluoromethylphenylsulfone, and tris(trichloromethyl)-s-1-lyazine. compounds, peroxides such as di-t-butyl peroxide, and the like.

These photopolymerization initiators may be used alone or in combination of two or more, and are preferably 0.1 to 20 parts by weight, particularly 0.1 to 20 parts by weight, based on 100 parts by weight of the solid content of the liquid photosensitive resin composition.
It is preferable to use 2 to 10 parts by weight. If it is less than 0.1 part by weight, sensitivity decreases, and if it exceeds 20 parts by weight, precipitation of crystals and insufficient hardening of the lower part occur.

Thermosetting catalysts for thermally reacting epoxy groups include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropyltriamine), bis(hexamethylene)triamine, 1.3.6-)risamino Polyamines such as methylhexane, polymethylene diamines such as trimethylhexamethylene diamine, polyether diamine, diethylaminoprobylamine, menthene diamine, infron diamine, bis(4-amino-3-methylcyclohexyl)methane and N - Aliphatic primary amines such as alicyclic polyamines such as aminoethylpiperazine, aromatic primary amines such as metaphenylenediamine, diaminophenylmethane, diaminophenyl sulfone and aromatic diamine eutectic mixtures, polyamine epoxy resin adducts , polyamine-ethylene oxide duct, polyamine-propylene oxide duct, cyanoethylated polyamine, modified amine such as ketoimine, tertiary amine such as piperidine, piperazine, morpholine, and tetramethylguanidine, triethanolamine, benzyldimethylamine, 2 4. Amine compounds such as tertiary amines such as 6-tris(dimethylaminomethyl)phenol, phthalic anhydride, trimellitic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerin tris(
anhydrotrimellitate), pyromellitic anhydride, 3
．． Aromatic acid anhydrides such as 3',4,4'-benzophenonetetracarboxylic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, enru succinic anhydride, hexahydrophthalic anhydride acids, cyclic aliphatic acid anhydrides such as methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, aliphatic acid anhydrides such as polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, and Acid anhydrides such as chlorendic anhydride, halogenated acid anhydrides such as tetrabromo-phthalic anhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-
Undecylimidazole, 2-heptadecylimidazole, 2-phenylimitasol, 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 incyanurate, 2-phenylimidazolium・Isocyanurate, 2,4-diamino-6-[
2-Methylimidazolyl-(I)]-]ethyl-8-triazine2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(I)]-dithyl-S-)riazine, 2,4-diamino -6-[2-Undecylimidazolyl-(I))-ethyl-8-triazine, 2-phenyl-4-methyl-5-t=)'roxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole , 1-cyanoethyl-2-phenyl-4,5-di(
Imidazole compounds such as cyanoethoxymethyl)imidazole, ■-dodecyl-2-methyl-3-benzylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride, novolac type phenolic resin, cresol type phenolic resin, resorcinol type phenolic resins and phenols such as polyvinylphenol, Lewis acid-amine complexes such as boron trifluoride-amine complexes, boron pentafluoride-amine complexes and arsenic pentafluoride-amine complexes, dicyandiamide, 0
-) rilbiguanide, phenylbiguanide and α-2
, dicyandiamide derivatives such as 5-dimethylbiguanide, organic acid hydrazides such as succinic acid hydrazide, adipic acid hydrazide, isophthalic acid hydrazide and p-oxybenzoic acid hydrazide, diaminomaleonitrile derivatives such as diaminomaleonitrile and benzyldiaminomaleonitrile, Known epoxy curing accelerators such as melamine and melamine derivatives such as N,N-diallylmelamine, amine imide derivatives, and polymercaptans can be used.

These thermosetting catalysts may be used alone or in combination of two or more, and are preferably 0.01 to 10 parts by weight, particularly 0.01 to 10 parts by weight, based on 100 parts by weight of solid content of the liquid photosensitive resin composition.
It is preferable to use 1 part of 05-5 weight. If it is less than 0.01 part by weight, the strength of the cured film will be insufficient, and if it exceeds 10 parts by weight, precipitation of crystals and a decrease in stability of the liquid will occur.

Examples of organic solvents used in the present invention include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, calpitols such as calpitol and butyl cavitol, and acetic acid ethynopeacetic acid. Examples include acetic acid esters such as butyl, cellosolve acetate, butyl cellosolve acetate, carpitol acetate, and butyl carpitol acetate.

The amount of these organic solvents is preferably 10 to 50 parts by weight, particularly 20 to 50 parts by weight, based on 100 parts by weight of the liquid photosensitive resin composition.
Preferably, 40 parts by weight are used. If it is less than 10 parts by weight, the liquid viscosity will be high, and if it exceeds 50 parts by weight, the liquid viscosity will be low and workability will decrease in either case.

The liquid photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor to prevent polymerization during drying. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pt-butylcatechol, 2.6-
Aromatic hydroxy compounds such as di-t-butyl-p-cresol, β-naphthol, and pyrogallol; quinones such as benzoquinone and p-toluquinone; amines such as naphthylamine, pyridine, p-toluidine, and phenothiazine;
Examples include aluminum salt or ammonium salt of N-nitron phenylhydroxylamine, floranil, nitrobenzene, and the like.

Furthermore, the liquid photosensitive resin composition of the present invention includes a tackifier, an adhesion promoter, a dispersant, a plasticizer, an anti-sagging agent, a leveling agent, an antifoaming agent, a flame retardant, a brightening agent, a coloring agent, etc. Supplementary additives may be added as necessary.

Examples of the tackifier or adhesion promoter include alkylphenol/formaldehyde novolac resin, polyvinyl butyral, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene,
Examples include styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, acrylic resin adhesive, aromatic, aliphatic, or alicyclic petroleum resin.

Addition of a tackifier or adhesion promoter increases the adhesion of the photosensitive resin to the substrate after photocuring, and this effect is particularly significant when used for copper printed wiring boards and solder printed wiring boards. .

A dispersant is used to improve the dispersibility, storage stability, etc. of a liquid photosensitive composition. The necessity of blending plasticizers, anti-sagging agents, leveling agents, and antifoaming agents depends on the method of using the liquid photosensitive resin composition, that is, the method of creating a coating film of the liquid photosensitive resin composition, and depends on the type used. and the amount is selected accordingly.

A single compound of these auxiliary additives may not only exhibit one type of property (dispersibility, plasticity, anti-sagging, leveling or antifoaming properties), but may also exhibit multiple additive effects. For example, dispersants may also act as plasticizers, leveling agents, and antifoaming agents in liquid photopolymer compositions, and dispersants, anti-sag agents, leveling agents, and antifoaming agents may also act as plasticizers, leveling agents, and antifoaming agents in liquid photopolymer compositions, and dispersants, anti-sag agents, leveling agents, and antifoaming agents may also act as plasticizers, leveling agents, and antifoaming agents in liquid photosensitive resin compositions; It also has an effect on the glossiness of resin compositions, and may act as a brightening agent.

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 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, diaryl 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.

As the anti-sag agent, inorganic fine powder such as talc, mica, silicon dioxide, titanium dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, etc. is used.

Examples of coloring agents include inorganic pigments such as titanium oxide, carbon black, and iron oxide, organic dyes such as methylene chloride, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes, and phthalocyanine dyes such as phthalocyanine blue and phthalocyanine green. Alternatively, an azo-based FB pigment is used.

Examples of flame retardants include non-organic flame retardants such as antimony trioxide, zirconium hydroxide, barium metaborate, magnesium hydroxide, and aluminum hydroxide; Halogen-based products such as perchloropentacyclodecane, tetrabromobenzene, and diphenyl chloride!
#Flameants, and chlorinated phosphonitrile derivatives, vinyl phosphonates, allyl phosphonates, tris(β-
Phosphorous flame retardants such as chloroethyl) phosphonate, tricresyl phosphonate, and ammonium phosphate are used.

When forming an image using the liquid photosensitive resin composition of the present invention obtained in this manner, the liquid photosensitive resin composition is applied to a substrate, heated and cured to make the surface non-adhesive, and then The method of applying the liquid photosensitive resin composition of the present invention onto a substrate by applying a pattern mask to the cured coating film, exposing it to light, developing it with an alkaline aqueous solution, and eluting the uncured film to obtain an image includes, for example, spraying. method, dip method, brush coating method, roller coating method, flow coater method, curtain coating method, screen printing method, etc.
In particular, for coating printed wiring boards, thin metal films, etc., roller coating methods, curtain coating methods, screen printing methods, etc. are preferred.

The liquid photosensitive resin composition of the present invention can be cured using both heat and light. In particular, when used as a photoresist, the coating film is cured by heating before irradiation with actinic rays. Eliminates the stickiness of the membrane surface. The heat curing conditions at this time are preferably, for example, 70 to 120°C for 5 to 30 minutes. As a result of heating and curing in this manner, it becomes non-adhesive, and it becomes possible to expose the cured coating film with a pattern mask in close contact with it.

Examples of the exposure light source used for photocuring the liquid photosensitive resin composition of the present invention include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, laser beams, etc., and 300 ntn
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 rays around 400 T1rl'l.

The liquid photosensitive 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, but in some cases. , amines such as primary amines such as butylamine, hexylamine, benzylamine, allylamine, secondary amines such as diethylamine and benzylethylamine, tertiary amines such as triethylamine,
Hydroxylamines such as ethanolamine, jetanolamine, triethanolamine, 2-amino to 1゜3-prowinterpanediol, cyclic amines such as morpholine, pyridine, piperazine, piperidine, etc., polyamines such as hydrazine, ethylenediamine, hexamethylenediamine, etc. ,
Basic salts of the amines such as sulfates, carbonates, bicarbonates, alkali metal phosphates, pyrophosphates, quaternary ammonium salts such as tetramethylammonium hydroxide, choline hydroxide, etc. can also be used. .

Further, the liquid photosensitive resin composition of the present invention can be used after image formation.
By post-curing by heat treatment as necessary,
It is also possible to form a cured film with improved heat resistance. The conditions at this time are preferably, for example, 120 to 170°C for 10 to 60 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.

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

(Synthesis Example-1) 100 parts of vinyl polymer of 4-vinylphenyl glycidyl ether, 51.3 parts of methacrylic acid, 0 fetchazine
．． 11N was dissolved in 101.7 parts of carpitol acetate, and 1.1N of benzyltriethylammonium chloride was dissolved.
Add 3 parts and stir at 80°C for 12 hours.

Tetrahydrophthalic anhydride 846B was added to this reaction product, and the mixture was stirred at 80°C for 4 hours to obtain modified polystyrene resin 1.

(Synthesis Example-2) Carpitol acetate [01°7 parts of Synthesis Example-1 was converted to 89
．． Modified polystyrene resin 2 was obtained in the same manner as in Synthesis Example 1, except that 84.6 parts of tetrahydrophthalic anhydride was replaced with 55.7 parts of succinic anhydride.

(Synthesis example-3) Ebicuron N-673 (Dainippon Ink @ cresol novolac type epoxy resin epoxy equivalent 210) 10
0 parts, 35.7 parts of acrylic acid, 0.07 parts of hydroquinone
1.07 parts of benzyltriethylammonium chloride was added to the solution, and the mixture was stirred at 80°C for 12 hours.

By adding 704 parts of tetrahydrophthalic anhydride to this reaction product and stirring at 80°C for 4 hours, the polymerizable resin 3.
I got it.

(Synthesis Example-4) 88.8 parts of carpitol acetate of Synthesis Example-3 was added to 78
．． 4 parts, 70.4 parts of tetrahydrophthalic anhydride and 46.4 parts of succinic anhydride. Polymerizable resin 4 was obtained in the same manner as in Synthesis Example 3 except that -28 was used.

(Example-1) <Component M> 1350 parts of the modified polystyrene resin obtained in Synthesis Example-1 15 parts of Florene rAc-3Q OJ (antifoaming agent Nphthalocyanine manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
Green 2.5 part Irgakinia 907
27.5 parts (photopolymerization initiator manufactured by Ciba Geigy) Silica 5 parts Barium sulfate 90 parts 1-benzyl-2-methylimidazole 10 parts Ingredients N > Triglycidyl 100 parts Incyanurate Dipentaerythritol 361 ffl Hexa Acrylate talc 14 parts Cellosolve acetate 50 parts Ingredients N Total
200 parts of the above components MSN were individually kneaded using a roll mill to prepare an ink.

Next, component M and component N were kneaded to obtain a liquid photosensitive resin composition.

(Comparative Example-1) A liquid photosensitive resin composition was prepared in the same manner as in Example-1 except that the polymerizable resin 3 obtained in Synthesis Example-3 was used instead of the modified polystyrene resin 1 in Example-1. Obtained.

(Example-2) A liquid photosensitive resin composition was obtained in the same manner as in Example-1 except that modified polystyrene resin 2 obtained in Synthesis Example-2 was used instead of modified polystyrene resin 10 in Example-1. Ta.

(Comparative Example-2) A liquid photosensitive resin composition was prepared in the same manner as in Example-1 except that polymerizable resin 4 obtained in Synthesis Example-4 was used instead of modified polystyrene resin 1 in Example-1. Obtained.

Table 1 shows the results of evaluating the performance of these liquid photosensitive resin compositions by the following method.

(2) Formation of coating film The copper-clad laminate is pretreated by polishing, cleaning, and removing moisture. A liquid photosensitive resin composition adjusted under various conditions was applied to the entire surface of the pretreated copper-clad laminate using a screen printing method, and dried at 70°C for 30 minutes in a hot air circulation drying oven to obtain a coating film. Ta.

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

■Evaluation of sensitivity A step wedge with a density difference of 0.15 (ΔlogE) was brought into close contact with the paint film, and a 5KW ultra-high pressure mercury lamp was used to illuminate the film for 1000 m/j/
A negative image corresponding to the wedge was obtained by exposing the film to light of cm2 and developing it for twice the time taken for the coating film to dissolve.The number of stages at which the image was completely dissolved (clear stage number) was determined.

■、Continuous exposure with an exposure amount that makes the pencil hardness evaluation clear stage number 12 steps、Developed in the same way as ■、50℃ at 140℃ in a hot air drying oven
After curing for a few minutes, measurements were made according to JIS K 5400 6-14.

■ Evaluation of adhesion In the same way as the evaluation of pencil hardness, perform exposure, development, and post-curing.
A substrate test was conducted according to JIS K 5400 6-15.

■ Evaluation of insulation resistance ['C-B-25 Except that a double-sided copper-clad laminate with a test pattern formed thereon was used, exposure, development, and post-curing were performed in the same manner as the pencil hardness evaluation method, and in accordance with JISZ 3197. , the insulation resistance was determined using rTR-8 manufactured by Atopan Test Co., Ltd.
Using 601J, the resistance value was measured 1 minute after applying 500V DC.

■、Solvent resistance evaluationSimilar to the insulation resistance evaluation, perform exposure, development, and post-curing.
The sample was immersed in 1.1.1-) dichloroethane at 20° C. for 1 hour, and then the state and adhesion of the coating film were comprehensively evaluated.

■ Evaluation of Acid Resistance Similar to solvent resistance, exposure, development, and post-curing were performed, and the sample was immersed in a 1Qvo 1% sulfuric acid aqueous solution at 20°C for 30 minutes, and then the condition and adhesion of the coating film were evaluated. Judgment was made comprehensively.

(Effects of the Invention) As is clear from the above examples, the liquid photosensitive resin composition of the present invention, after being applied to a printed wiring board, is dried by heating to eliminate the tackiness of the coating film surface and allow the pattern mask to adhere tightly. It has high sensitivity and can be developed with an alkaline aqueous solution.

Further, the composition has excellent electrical properties, mechanical properties, and chemical resistance by thermosetting after development, and is a liquid photosensitive resin composition that can be used as a permanent protective mask for printed wiring boards.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (spontaneous)

Claims (1)

[Scope of Claims] (A) A polymer having a repeating unit of the following general formula (I), a compound having a carboxyl group and an ethylenically unsaturated double bond in the same molecule, and a saturated or unsaturated polybase General formula (I) of a modified polystyrene resin obtained by sequentially reacting acid anhydrides ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R means hydrogen or a methyl group, and Ar means phenylene or substituted phenylene. (B) Polymerizable compound having at least one ethylenically unsaturated double bond (C) Epoxy compound having at least one epoxy group (D) Photoinitiator or photoinitiator system (E) A liquid photosensitive resin composition containing a thermosetting catalyst (F) an organic solvent that causes an epoxy group to undergo a thermal reaction.