JP2554275B2 - Liquid photosensitive resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid photosensitive resin composition, and more specifically, it can be used for forming a permanent protective mask such as a solder resist for producing a printed wiring board. The present invention relates to a liquid photosensitive resin composition capable of both photocuring and heat curing, which has high sensitivity to ultraviolet light exposure and has excellent electrical properties and chemical resistance of a coating film after curing.

(Prior art) Conventionally, in the printed wiring board industry, solder resist,
Resin compositions used for permanent protection masks such as resists for chemical plating are mainly composed of thermosetting resins such as epoxy resins and melamine resins, and screen printing is often used for pattern formation. Have been. The main purpose of the solder resist is to limit the soldering area at the time of soldering, prevent solder bridges, etc., prevent corrosion of the conductors, and maintain electrical insulation between the conductors for a long period of time.

However, in recent years, along with the high-density mounting of VLSI and the like, it has been required to reduce the conductor spacing, the demand for electrical insulation between conductors is strict, and solder resists and the like with excellent dimensional accuracy are also required. However, the three-screen printing method has an inherently low resolution, and it may cause blurring, pinholes (for high-viscosity ink) or bleeding, bleeding,
Phenomenon such as sagging (in the case of low viscosity) has occurred, and it is becoming difficult to cope with higher density of printed wiring boards.

Therefore, a pattern can be formed by a photographic method (an image is formed by development following image exposure), which has high sensitivity, high resolution, and
At present, a photosensitive resin composition, which has excellent adhesion to a substrate and also has excellent electrical properties and mechanical properties of a coating film after curing, has been attracting attention.

Further, in recent years, a photosensitive resin composition that can be developed with an alkaline aqueous solution or water has been desired due to problems such as work environment, air and water pollution.

A dry film type or liquid developable photosensitive resin composition has been developed as a permanent protection mask for a printed wiring board to be patterned by a photographic method.

As a dry film type photosensitive resin composition, for example, a photosensitive resin composition comprising urethane di (meth) acrylate, a linear polymer compound and a photosensitizer in JP-A-57-55914 and the like, JP-A-62-247353 discloses a photosensitive resin composition comprising a (meth) acrylic modified resin of a specific novolac epoxy resin and a photosensitizer.

However, generally, in the case of a dry film type photosensitive resin composition, bubbles are likely to be generated during thermocompression bonding, and there is concern about heat resistance and adhesiveness. As disclosed in Japanese Laid-Open Patent Publication No. 52-52703,
A special process such as heating and pressure bonding under reduced pressure is required, and even if such a process is used, complete heat resistance and adhesion are not guaranteed.

On the other hand, a liquid developable photosensitive resin composition has a small number of steps because it is directly applied to a printed wiring board in a liquid state immediately before use. It can form an excellent image and is suitable as, for example, a photosensitive resin composition for a permanent protection mask for a printed wiring board having a narrow conductor interval.

However, this liquid photosensitive resin composition also has a drawback that the pattern mask is stained when exposed to light by directly applying the pattern mask to the coating film surface after coating on the printed wiring board.

As a method for solving the contamination of the pattern mask, as disclosed in JP-A-57-164595, a liquid photosensitive resin composition is applied to a printed wiring board and then dried to form a film. In contrast to the above method, there is a special method in which the pattern masks are arranged in a liquid state without being dried, with an interval therebetween, exposed to light and cured, and the uncured liquid photosensitive resin composition is removed. However, since dry film formation is not performed, it is necessary to provide a space between the surface of the coated liquid photosensitive composition and the pattern mask, and the resolution is deteriorated by that amount, and it is expensive because a special device is equipped. is there.

Further, JP-A-58-24144, 59-2049, etc., a liquid photosensitive resin composition is applied to a uniform thickness on a transparent flexible support or a pattern mask which transmits actinic rays,
Immediately, by moving the flexible support or the pattern mask and pressing the coated surface of the liquid photosensitive resin composition toward the printed wiring board with a constant pressure, the liquid photosensitive resin composition on the printed wiring board is fixed to a predetermined thickness. A method of manufacturing a solder resist is disclosed by stacking on a substrate, then exposing, peeling and developing a flexible support or a pattern mask. In this method, the liquid photosensitive resin composition is applied to a transparent flexible support or a pattern mask in a uniform thickness, and then, when the printed wiring board is pressed at a constant pressure, the printed wiring board is uneven. Therefore, there is a problem that air bubbles are entrained, a large number of air bubbles are generated in the image, heat resistance and adhesiveness are uncertain, and further, a specific device is required and the cost becomes high.

Furthermore, in JP-A-61-102652 and 62-27736,
After applying the liquid photosensitive composition on the printed wiring board, pressing a transparent flexible support or pattern mask with a constant pressure,
A method for producing a solder resist by exposing through a pattern mask, peeling off the flexible support or the pattern mask, and then developing is disclosed. Also in these methods, there is a problem that a flexible support or a pattern mask is pressed with a constant pressure and a specific device for exposing is required, which is expensive.

Furthermore, in the method of exposing according to the resist pattern as it is, without drying the liquid photosensitive composition shown above, since the liquid photosensitive composition uses a liquid prepolymer containing a large number of reactive monomers, acid resistance However, there is also a problem that the properties such as chemical resistance are inferior to those of ordinary methods.

After applying a liquid photosensitive resin, it is heated and dried, a pattern mask is brought into close contact with light to expose it, and a method for forming a solder resist by developing is as disclosed in JP-A-61-243869. A liquid resist ink composition containing a novolac type epoxy compound, a compound obtained by reacting an unsaturated monocarboxylic acid and a polybasic acid anhydride,
There is a liquid resin composition containing a bisphenol type epoxy resin having an unsaturated group and a carboxyl group as a main component, as disclosed in JP-A-62-187722.

However, these liquid photosensitive resin compositions are also inadequate in sensitivity and properties such as electric properties and chemical resistance of the coating film after curing.

(Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned conventional technical problems and to form a photosensitive resin layer having a uniform thickness without bubbles on a printed wiring board, and By heating a printed wiring board coated with a photosensitive resin before exposure, the adhesiveness of the surface of the photosensitive resin coating film can be eliminated and the coating surface and the pattern mask can be closely contacted and exposed to light. Both thermosetting and thermosetting are possible, high sensitivity, electrical characteristics of the coating film after curing,
Another object of the present invention is to provide a liquid photosensitive resin composition which has excellent mechanical properties and chemical resistance and can be developed with an alkaline aqueous solution.

(Means for Solving Problems) The present inventors have found that the above problems can be solved by using the following liquid photosensitive resin composition, and arrived at the present application.

(A) A high-molecular polymer having a repeating unit of the following 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 anhydride are sequentially reacted. Modified polystyrene resin obtained by the general formula (I) (In the formula, R is hydrogen or a methyl group, Ar is phenylene,
Or, it means a substituted phenylene. ) (B) Polymerizable compound having at least one ethylenically unsaturated double bond (C) Epoxy compound having at least one epoxy group (D) Photopolymerization initiator or photopolymerization initiator system (E) Epoxy A liquid photosensitive resin composition containing a thermosetting catalyst (F) for organic reaction of a group, an organic solvent.

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

The modified polystyrene resin (A) is a high molecular polymer having a repeating unit of the 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. It is obtained by sequentially reacting anhydrides.

As the polymer having a repeating unit represented by the general formula (I), 4-vinylphenol, 4-isopropenylphenol, 2-ethyl-4-vinylphenol, 2-isopropyl-4-vinylphenol, 2,6- Diisopropyl-4-vinylphenol, 2,6-di-t-butyl-
Homopolymers such as 4-vinylphenol, 2,6-di-t-butyl-4-isopropenylphenol, brominated-4-vinylphenol, and brominated 4-isopropenylphenol, or a homopolymer copolymerizable therewith Examples thereof include copolymers with monomers. Among these, particularly preferable specific examples include poly (4-vinylphenol), poly (4-isopropenylphenol), 4-isopropenylphenol / acrylonitrile copolymer, and 4-vinylphenol /
A methyl methacrylate copolymer is mentioned.

Moreover, as a compound which has an epoxy group and an ethylenically unsaturated double bond in the same molecule, an epoxy alkyl (meth) acrylate is mentioned first. Such compounds include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-epoxypentyl acrylate, 4,5-epoxypentylmethacrylate,
5,6-epoxyhexyl acrylate, 5,6-epoxyhexyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 10,11
-Epoxy undecyl acrylate, 10,11-epoxy undecyl methacrylate, 4-glycidyl cyclohexyl acrylate, 4-glycidyl cyclohexyl methacrylate and the like can be mentioned. A 1: 1 addition reaction product of a diglycidyl ether compound and (meth) acrylic acid can also be used. Examples of the diglycidyl ether compound include bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, and diethylene glycol diglycidyl ether. Further, monoglycidyl ether mono (meth) acrylate of diol can also be used. Examples of the diol include bisphenol A, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, dipropylene glycol and ditetramethylene glycol. Further, monoglycidyl ester mono (meth) acryloxyethyl ester of dicarboxylic acid can also be used. Examples of the dicarboxylic acid include phthalic acid, cyclohexene dicarboxylic acid, cyclohexanedicarboxylic acid, maleic acid, malonic acid, succinic acid and the like. Also, 1-
Chloro-2,3-epoxypropyl acrylate, 1-chloro-2,3-epoxypropyl methacrylate, 2-bromo-3,4-epoxybutyl acrylate, 2-bromo-3,4-epoxybutyl methacrylate, 2- (epoxy Ethyloxy) -ethyl acrylate, 2- (epoxyethyloxy) -ethyl methacrylate, 2- (3,4
-Epoxybutyloxy) -ethyl acrylate, 2-
(3,4-Epoxybutyloxy) -ethylmethacrylate etc. can also be used. Of these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.

Further, as the saturated or unsaturated polybasic acid anhydride,
Succinic anhydride, methylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, ethylsuccinic anhydride, dodecenylsuccinic anhydride, nonenylsuccinic anhydride, maleic anhydride, methylmaleic anhydride, anhydrous 2,2.
3-dimethylmaleic acid, 2-chloromaleic anhydride,
2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaccot 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 anhydride such as-(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, 3,3 ', 4,4'
-Polybasic acid anhydrides such as benzophenone tetracarboxylic acid can be used. Of these, the above dibasic acid anhydrides are preferable, and succinic anhydride and tetrahydrophthalic anhydride are particularly preferable.

The modified polystyrene resins are obtained by sequentially reacting each of them, and the ratio of reacting them is such that the epoxy group in the same molecule is equivalent to the hydroxyl group of 1 equivalent of the polymer having the repeating unit of the general formula (I). Compound having an ethylenically unsaturated double bond 0.5 to 1.2 equivalents, preferably 0.8 to 1.1
The amount is equivalent to 0.1 to 1.1 equivalents of polybasic acid anhydride, preferably 0.3 to 1.0 equivalent. If the amount of the compound having an epoxy group and an ethylenically unsaturated double bond in the same molecule is less than 0.5 equivalent, the sensitivity is lowered, and if it exceeds 1.2 equivalent, the tackiness problem occurs. Further, if the polybasic acid anhydride is less than 0.1 equivalent, the developability is lowered and the resin is gelated. If it exceeds 1.1 equivalent, problems such as tackiness and crystal precipitation occur.

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

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

Examples of the monohydric alcohol in the ester of acrylic acid or methacrylic acid of monohydric or polyhydric alcohol include, for example, methanol, ethanol, propanol, isopropanol, 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 alcohol, polyethylene glycol monoethyl alcohol, 2-hydroxy-3-chloropropane, dimethylamino alcohol, diethylamino alcohol, glycidol, 2-trimethoxy. Examples thereof include silyl ethanol, ethylene chlorohydrin, ethylene bromohydrin, 2,3-dibromopropanol, allyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol and naphthol. Examples of the polyhydric alcohol include 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, cycloheptanediol, 1,4-cyclohexanedimethanol, 3-cyclohexene-1,1-diethanol, 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, decalin diol, 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-pentanediol,
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 -(1-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) -diethanolamine, N, N- Bis (2-hydroxyethyl) piperazine, 1,3-bis (hydroxymethyl) urea, 1,2-
Bis (4-pyridyl) -1,2-ethanediol, Nn
-Butyldiethanolamine, diethanolamine, N
-Ethyldiethanolamine, 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-trihydroxyhexane, 1,2,4-benzenetriol, triethanolamine, 2 2,2-bis (hydroxymethyl) -2,2 ′, 2 ″ -nitrilotriethanol and the like. Among these esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohols, ethylene glycol diacrylate and ethylene recall. Dimethacrylate, polyethylene Recall diacrylate, polyethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Pentamethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, neopentyl glycol diacrylate, neopentyl Call dimethacrylate, sorbitol hexaacrylate, sorbitol hexa methacrylate, sorbitol pentaacrylate, sorbitol pentaacrylate methacrylate are preferred.

It is also possible to use acrylamides or methacrylamides of monoamines or polyamines. Examples of the monoamine here include ethylamine,
Butylamine, amylamine, hexylamine, octylamine, cyclohexylamine, monoalkylamines such as 9-aminodecalin, monoalkenylamines such as allylamine, methallylamine, benzylamine, and aromatic amines such as aniline, toluidine, p-aminostyrene. Is mentioned. Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, hexamethylenebis (2-aminopropyl) amine, diethylenetriamine, triethylenetetraamine, polyethylenepolyamine, tris (2-amino). Ethyl) 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, methylenedi Examples include aniline, 2,4-bis (4-aminobenzyl) aniline, aminophenyl ether and the like.

Further, allyl compounds such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, benzoic acid, chlorobenzoic acid,
Mono- or polyallyl esters of mono- or polycarboxylic acids such as malonic acid, oxalic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, chlorendic acid and trimellitic acid, benzenedisulfonic acid, Mono- or polyallyl esters of mono- or polysulfonic acids such as naphthalenedisulfonic acid,
Diallylamine, N, N′-diallyl oxalic acid diamide,
1,3-diallyl urea, diallyl ether, triallyl isocyanurate and the like can also be used.

Further, for example, divinylbenzene, p-allylstyrene, p-isopyropenylstyrene, divinylsulfone,
It has a polyvinyl compound such as ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl succinate, divinyl phthalate and divinyl terephthalate, and an ionic group such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyphenyltrimethylammonium chloride. An ester compound of acrylic acid or methacrylic acid can also be used.

Further, commercially available polymerizable monomers or oligomers, for example, Alonix M5700, M6100, manufactured by Toagosei Chemical Industry Co., Ltd.
Acrylate monomers such as M8030, M152, M205, M215, M315, M325, NK ester ABPE manufactured by Shin Nakamura Chemical Co., Ltd.
4, U-4HA, CB-1, CBX-1, KAYARAD manufactured by Nippon Kayaku Co., Ltd.
R604, DPCA-30, DPCA-60, KAYAMAR PM-1, PM-2,
Acrylate or methacrylate monomers such as Sannopco's Photomer 4061, 5007, epoxy acrylates such as Showa Polymer's Lipoxy VR60, VR90, SP1509 etc., Spiro acetal structure such as Spyrac E-4000X, U3000 made by the same company and acrylic or methacrylic group It is also possible to use a spirane resin having and.

These compounds may be used alone or in combination of two or more, and preferably 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 be reduced, and if it exceeds 40 parts by weight, the electrical properties and mechanical properties of the cured film will be deteriorated.

Examples of the compound having at least one epoxy group used in the present invention include glycidyl ethers of alcohol having 2 to 20 carbon atoms such as butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, aryl glycidyl ether and phenyl glycidyl ether. , Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol Polyglycidyl ethers of polyols such as traglycidyl ether and polyglycerol polyglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 2,6,2 ′, 6′-tetramethyl-4,4′-biphenyldiglycidyl ether 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 resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, brominated epoxy resin and other glycidyl ether type epoxy compounds, alicyclic diepoxy acetal, alicyclic diepoxy adipate , Cyclic aliphatic epoxy compounds such as alicyclic diepoxy adipate and vinylcyclohexenedioxide, glycidyl acrylate, glycidyl methacrylate, tetrahydroxyphthalic acid diglycidyl ester, sorbic acid glycidyl ester, oleic acid glycidyl ester and linoleic acid glycidyl ester Unsaturated acid glycidyl esters, butyl glycidyl ester, octyl glycidyl ester, hexahydro Glycidyl esters such as alkyl carboxylic acid glycidyl esters such as thallic acid diglycidyl ester and dimer acid glycidyl ester, and benzoic acid glycidyl ester, aromatic carboxylic acid glycidyl esters such as o-phthalic acid diglycidyl ester and diglycidyl p-oxybenzoic acid Ester type epoxy compound, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m-xylylenediamine, diglycidyltribromoaniline and tetra Glycidyl amine type epoxy compounds such as glycidyl bisaminomethylcyclohexane, diglycidyl hydantoin, glycidyl glycidoxyal Ruhidantoin and heterocyclic epoxy compounds such as triglycidyl Gilles isocyanurate. Of these, 2,6,
2 ', 6'-Tetramethyl-4,4'-biphenyldiglycidyl ether, novolac type epoxy resin, and heterocyclic epoxy compound are preferable.

These epoxy compounds may be used alone or in admixture of two or more, and preferably 1 to 40 parts by weight, particularly 5 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 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.

As the photopolymerization initiator used in the present invention, for example, benzyl, α-diketones such as diacetyl, acyloins such as benzoin, benzoin methyl ether, benzoin ethyl ether, acyloin ethers such as benzoin isopropyl ether, thioxanthone, 2 Thioxanthones such as 4,4-diethylthioxanthone, thioxanthone-1-sulfonic acid and thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino)
Benzophenones such as benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxyacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) Phenyl] -2-morpholino-1-propanone and other acetophenones and anthraquinones, 1,4-naphthoquinone and other quinones, phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-
Examples thereof include halogen compounds such as triazine and peroxides such as di-t-butyl peroxide.

These photopolymerization initiators may be used alone or in admixture of two or more, and are preferably 0.1 to 20 parts by weight, particularly 0.2 to 10 parts by weight, based on 100 parts by weight of the solid content of the liquid photosensitive resin composition. Preference is given to using. If it is less than 0.1 part by weight, the sensitivity will be lowered, and if it exceeds 20 parts by weight, crystals will be precipitated and the lower part will be insufficiently cured.

Thermosetting catalysts for thermally reacting epoxy groups include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropyltriamine), bis (hexamethylene) triamine, 1,3,6-trisaminomethyl. Polyamines such as hexane, trimethylhexamethylenediamine, polyetherdiamine, polymethylenediamines such as diethylaminopropylamine, menthenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane and N-aminoethyl Aliphatic primary amines such as alicyclic polyamines such as piperazine, metaphenylene diamine, diaminophenylmethane, diaminophenyl sulfone and aromatic diamines such as eutectic mixtures of aromatic diamines, polyamines Epoxy resin adduct, a polyamine - ethylene oxide adduct, a polyamine - propylene oxide adducts, cyanoethylated polyamine,
Modified amines such as ketoimine, piperidine, piperazine,
Secondary amines such as morpholine, and amine compounds such as tetramethylguanidine, triethanolamine, benzyldimethylamine, tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, phthalic anhydride, Trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerin tris (anhydro trimellitate), pyromellitic dianhydride, 3,3 ', 4,
Aromatic acid anhydrides such as 4′-benzophenone tetracarboxylic acid anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride,
Endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride and other cyclic aliphatic acid anhydrides, polyadipic acid Aliphatic acid anhydrides such as anhydrides, polyazelaic acid anhydrides and polysebacic acid anhydrides, and acid anhydrides such as chlorendic acid anhydrides and halogenated acid anhydrides such as tetrabromophthalic anhydride, 2-methylimidazole , 2-ethyl-4-
Methylimidazole, 2-undecylimidazole, 2
-Heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-undecyl imidazole , 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-triazine, 2,4-diamino-
6- [2-ethyl-4-methylimidazolyl- (1)]
-Ethyl-S-triazine, 2,4-diamino-6- [2
-Undecylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl- 4,5-di (cyanoethoxymethyl) imidazole,
Imidazole compounds such as 1-dodecyl-2-methyl-3-benzylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride;
Phenols such as novolak type phenolic resin, cresol type phenolic resin, resorcinol type phenolic resin and polyvinyl phenol, Lewis acids such as boron trifluoride-amine complex, boron pentafluoride-amine complex and arsenic pentafluoride-amine complex Amine complexes, dicyandiamide, o-tolylbiguanide, dicyandiamide derivatives such as phenylbiguanide and α-2,5-dimethylbiguanide, organic acid hydrazides such as succinic hydrazide, adipic hydrazide, isophthalic hydrazide and p-oxybenzoic hydrazide. , Diaminomaleonitrile, benzyldiaminomaleonitrile and other diaminomaleonitrile derivatives, melamine and N, N-diallylmelamine and other melamine derivatives, amine imide derivatives, polymercaptans It can be used in the known epoxy curing accelerator.

These thermosetting catalysts may be used alone or as a mixture of two or more, and are preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the liquid photosensitive resin composition. Preferably. If it is less than 0.01 parts by weight, the strength of the cured film will be insufficient, and if it exceeds 10 parts by weight, crystals will precipitate and the stability of the liquid will be reduced.

The organic solvent used in the present invention, methyl ethyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve, cellosolves such as butyl cellosolve, carbitol, carbitols such as butyl cavitol, acetic acid. There are acetic acid esters such as ethyl, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate and butyl carbitol acetate.

These organic solvents are preferably used in an amount of 10 to 50 parts by weight, particularly preferably 20 to 40 parts by weight, based on 100 parts by weight of the liquid photosensitive resin composition. If it is less than 10 parts by weight, the liquid viscosity is high, and if it exceeds 50 parts by weight, the liquid viscosity is low, and the workability is deteriorated.

It is preferable to add a thermal polymerization inhibitor to the liquid photosensitive resin composition of the present invention in order to prevent polymerization during drying. As the thermal polymerization inhibitor, for example, 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, N-nitrosophenyl Aluminum hydroxide or ammonium salt of hydroxylamine, floranyl, nitrobenzene and the like can be mentioned.

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, a defoaming agent, a flame retardant, a glossing agent, a coloring agent, etc. You may mix the auxiliary additive of this as needed.

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

The addition of the tackifier or the adhesion promoter enhances the adhesion of the photosensitive resin after photo-curing to the substrate, and particularly when used for a copper printed wiring board and a solder printed wiring board, the effect is greatly exhibited. .

The dispersant is used to improve dispersibility, storage stability and the like of the liquid photosensitive composition. The necessity of blending a plasticizer, an anti-sagging agent, a leveling agent, and an antifoaming agent depends on the method of using the liquid photosensitive resin composition, that is, the method of forming a coating film of the liquid photosensitive resin composition, and the type used. And the amount is selected appropriately.

These supplementary additives may not only exhibit one kind of property (dispersibility, plasticity, anti-sagging, leveling or defoaming properties), but may also exhibit a plurality of additive effects. For example, the dispersant may also act as a plasticizer, a leveling agent and an antifoaming agent for the liquid photosensitive resin composition, and the dispersant, the anti-sagging agent, the leveling agent and the antifoaming agent may be used as a photosensitizer after photocuring. It also has an effect on the glossiness of the resin composition and may act as a brightener.

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

As the plasticizer, for example, ethylene glycol diphthalate, diethylene glycol diphthalate, ethylene glycol dicaprate, glycol esters such as diethylene glycol dicaprate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diaryl phthalate,
Phthalates such as butylbenzyl phthalate, phosphates such as triphenyl phosphate and tricresyl phosphate, diethyl malate, dibutyl adipate, triethyl citrate, ethyl laurate and the like are used.

As the anti-sagging agent, for example, inorganic fine powder such as talc, mica, silicon dioxide, titanium dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate and the like are used.

Examples of the coloring agent include inorganic pigments such as titanium oxide, carbon black, and iron oxide; organic dyes such as methylene blue, crystal violet, rhodamine B, fuchsin, auramine, azo dyes, and anthraquinone dyes;
A phthalocyanine-based or azo-based organic pigment such as phthalocyanine blue and phthalocyanine green is used.

Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, zirconium hydroxide, barium metaborate, magnesium hydroxide, and aluminum hydroxide, tetrabromobisphenol A, chlorinated paraffin, perchloropentacyclo. Halogen-based flame retardants such as decane, tetrabromobenzene, chlorinated diphenyl, and chlorophosphonitrile derivatives, vinylphosphonates, allylphosphonates, tris (β-chloroethyl) phosphonates, tricresylphosphonates, Phosphorus flame retardants such as ammonium phosphate are used.

When an image is formed using the liquid photosensitive resin composition of the present invention thus obtained, the liquid photosensitive resin composition is applied to a substrate and then heat-cured to make the surface non-tacky, and then A pattern mask is brought into close contact with the cured coating film, exposed to light, and developed with an alkaline aqueous solution to elute the uncured film to obtain an image.

Examples of the method for applying the liquid photosensitive resin composition of the present invention onto a substrate include a spray method, a dipping method, a brush coating method, a roller coating method, a flow coater method, a curtain coating method, a screen printing method and the like. In particular, a roller coating method, a curtain coating method, a screen printing method and the like are preferable for coating a printed wiring board, a thin film metal or the like.

The liquid photosensitive resin composition of the present invention can be cured by using either heat or light, and particularly when it is used as a photoresist, the coating film is heated and cured before being irradiated with actinic rays. The tackiness of the film surface is lost. The conditions for heat curing at this time are, for example, preferably 70 to 120 ° C. and 5 to 30 minutes. As a result of heat-curing in this way, it becomes non-adhesive, and it becomes possible to bring a pattern mask into close contact with the cured coating film for exposure.

Examples of the exposure light source used for photocuring the liquid photosensitive resin composition of the present invention include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp and a laser beam, but 300 nm to 400 nm.
It is preferable to use an exposure device that uses a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp that emits ultraviolet rays in the vicinity of nm as a light source.

The liquid photosensitive resin composition of the present invention can be developed with an aqueous alkaline 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 or the like can be used, but in some cases, amine Examples, primary amines such as butylamine, hexylamine, benzylamine and allylamine, secondary amines such as diethylamine and benzylethylamine, tertiary amines such as triethylamine,
Hydroxylamines such as ethanolamine, diethanolamine, triethanolamine, 2-amino-1,3-propanediol, cyclic amines such as morpholine, pyridine, piperazine and piperidine, polyamines such as hydrazine, ethylenediamine and hexamethylenediamine, It is also possible to use basic salts such as sulfates, carbonates, bicarbonates, alkali metal phosphates and pyrophosphates, and quaternary ammonium salt hydroxides such as tetramethylammonium hydroxide and choline.

In addition, the liquid photosensitive resin composition of the present invention can also be post-cured by heat treatment as necessary after image formation to form a cured film having more improved heat resistance.
The conditions at this time are, for example, preferably 120 to 170 ° C. and 10 to 60 minutes.

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

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Unless otherwise specified, parts are parts by weight
Represents

(Synthesis Example-1) 100 parts of resin ML (poly (4-vinylphenol) manufactured by Maruzen Petroleum Co., Ltd.), 116 parts of glycidyl methacrylate, and 0.15 part of phenothiazine were dissolved in 144 parts of carbitol acetate, and benzyltriethylammonium chloride 1.
Add 9 parts and stir at 80 ° C. for 12 hours.

120.2 parts of tetrahydrophthalic anhydride 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) 144 parts of carbitol acetate of Synthesis Example-1 was added to 127 parts, and 120.2 parts of tetrahydrophthalic anhydride was added to 7 parts of succinic anhydride.
Modified polystyrene resin 2 was obtained in the same manner as in Synthesis Example-1 except that the content was changed to 9 parts.

(Synthesis example-3) Epiclon N-673 (Dainippon Ink and Chemicals, Inc. cresol novolac type epoxy resin, epoxy equivalent 210) 100
Parts, acrylic acid 35.7 parts, and hydroquinone 0.07 parts are dissolved in carbitol acetate 88.8 parts, benzyltriethylammonium chloride 1.07 parts is added, and the mixture is stirred at 80 ° C. for 12 hours.

70.4 parts of tetrahydrophthalic anhydride was added to this reaction product, and the mixture was stirred at 80 ° C. for 4 hours to obtain a polymerizable resin 3.

(Synthesis Example-4) 88.8 parts of carbitol acetate of Synthesis Example-3 was added to 78.4 parts, and 70.4 parts of tetrahydrophthalic anhydride was added to succinic anhydride 4
Polymerizable resin 4 was obtained in the same manner as in Synthesis Example-3 except that the amount was changed to 6.2 parts.

(Example-1) <Component M> Modified polystyrene resin 1 obtained in Synthesis Example-1 350 parts Floren "AC-300" 15 parts (Antifoaming agent manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) Phthalocyanine green 2.5 parts Irgacure 907 27.5 parts (photopolymerization initiator manufactured by Ciba-Geigy) Silica 5 parts Barium sulfate 90 parts 1-Benzyl-2-methylimidazole 10 parts Ingredient M Total 500 parts <Ingredient N> Triglycidyl 100 parts Isocyanurate Dipentaerythritol 36 parts Hexaacrylate Talc 14 parts Cellosolve acetate 50 parts Component N Total 200 parts The above components M and N were separately kneaded by a roll mill to prepare an ink.

Next, the component M and the 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 prepared in the same manner as in Example-1 except that the modified polystyrene resin 2 obtained in Synthesis Example-2 was used instead of the modified polystyrene resin 1 of Example-1. Obtained.

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

The results of evaluating the performance of these liquid photosensitive resin compositions by the following methods are shown in Table 1.

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

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

, Evaluation of sensitivity A step wedge with a density difference of 0.15 (ΔlogE) was adhered to the coating film, exposed to 1000 mj / cm ² with a 5KW ultra-high pressure mercury lamp, and developed at a time twice as long as the coating film was dissolved to form a wedge. Corresponding negative images were obtained and the number of steps (clear steps) in which the image was completely eluted was examined.

, Pencil hardness evaluation Solid exposure was carried out at an exposure amount that the clear step number was 12, and after development in the same manner as above, it was post-cured at 140 ° C for 50 minutes in a hot air drying oven and measured according to JIS K 5400 6-14. did.

Evaluation of Adhesion Like the evaluation of pencil hardness, exposure, development and post-curing were performed, and a cross-cut test was performed according to JIS K 5400 6-15.

, Evaluation of insulation resistance Except that a double-sided copper clad laminate with an IPC-B-25 test pattern was used, exposure, development and post-curing were performed in the same manner as in the pencil hardness evaluation method, and insulation was performed according to JIS Z 3197. Resistance is measured by using "TR-8601" manufactured by Advantest Co., Ltd.
After applying DC500V, the resistance value at 1 minute was examined.

, Evaluation of solvent resistance Similar to the evaluation of insulation resistance, exposure, development and post-curing were performed, and the sample was immersed in 1,1,1-trichloroethane at 20 ° C for 1 hour. Adhesion was evaluated comprehensively.

, Evaluation of acid resistance Similar to solvent resistance, exposure, development and post-curing were performed, and the sample was immersed in a 10 vol% sulfuric acid aqueous solution at 20 ° C for 30 minutes. It was decided.

(Effect of the invention) As is clear from the above examples, the liquid photosensitive resin composition of the present invention is applied to a printed wiring board and then dried by heating to eliminate the tackiness of the coating film surface and bring the pattern mask into close contact. Can be exposed It has high sensitivity and can be developed with an alkaline aqueous solution.

Furthermore, it is a liquid photosensitive resin composition which is a composition excellent in electrical properties, mechanical properties and chemical resistance after development by thermosetting and which can be used as a permanent protection mask for printed wiring boards.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-49-2601 (JP, A) JP-A-63-11930 (JP, A) JP-A-63-278052 (JP, A) JP-A-64- 6014 (JP, A) JP-A-1-203424 (JP, A) JP-A-2-43551 (JP, A) JP-A-2-166452 (JP, A) JP-A-2-294371 (JP, A)

Claims (1)

(57) [Claims] 1. A polymer having a repeating unit represented by the following 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. Modified polystyrene resin obtained by sequentially reacting anhydrides General formula (I) (In the formula, R is hydrogen or a methyl group, Ar is phenylene,
Or, it means a substituted phenylene. ) (B) Polymerizable compound having at least one ethylenically unsaturated double bond (C) Epoxy compound having at least one epoxy group (D) Photopolymerization initiator or photopolymerization initiator system (E) Epoxy A liquid photosensitive resin composition containing a thermosetting catalyst (F) for organic reaction of a group, an organic solvent.