JP2003177534A - Photosensitive resin composition for image formation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for image formation having improved anti-tackiness of a preliminarily dried film, capable of improving electrical properties by a lowered dielectric constant and suitable for a solder resist, an etching resist and an electroless plating resist for production of a printed wiring board, an insulating layer of a build-up process printed wiring board, a black matrix, a color filter, photo-spacers, electrodes, barrier ribs and a phosphor for production of a liquid crystal display panel, a printing plate, etc. <P>SOLUTION: The photosensitive resin composition comprises a curable resin having two or more radical-polymerizable unsaturated bonds and one or more hydroxyl groups and/or carboxyl groups per molecule, a compound having two or more vinyl ether groups and/or vinyl thio-ether groups per molecule and a photopolymerization initiator. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition for image formation. Specifically, solder resist for printed wiring board manufacturing, etching resist, electroless plating resist, insulation layer of build-up method printed wiring board,
The present invention relates to a photosensitive resin composition for image formation suitable for a black matrix, a color filter, a photo spacer, an electrode, a partition wall, a phosphor, a printing plate, etc. for producing a liquid crystal display plate.

[0002]

2. Description of the Related Art Photosensitive resin compositions for image formation are photocurable and have the property that the uncured portion is dissolved by alkali or the like, and are used in various applications such as liquid development type resists. It is used. When such a photosensitive resin composition for image formation is used in, for example, a photolithography step of a substrate, a resist is first applied on the substrate and pre-dried to form a coating film, and then this coating film is formed. A pattern of the photocured resist is formed on the substrate by a series of steps of mounting a pattern forming film on the substrate, exposing it, and developing it.

In such a process, if tackiness remains in the coating film after heating and drying, a part of the resist adheres to the pattern-forming film after peeling, which makes it impossible to accurately reproduce the pattern. However, there is a problem that the pattern forming film cannot be peeled off. For this reason,
The tack-free property after forming a coating film is an important required property of a liquid development type resist.

Japanese Unexamined Patent Publication No. 64-22968 discloses a curable mixture based on a hydroxyl group-containing compound, a curable compound containing at least two enol ether groups, a catalyst and the like. However, this curable mixture is used for the production of molded products or coatings, or as a component of paints or adhesives, and is not intended to have photocurability. ,
There has been room for devising it so that it can be suitably used as a photosensitive resin composition for image formation.

In Japanese Patent Laid-Open No. 6-166843,
We proposed a photocurable liquid solder resist ink composition containing a novolac type epoxy resin, (meth) acrylic acid, a photopolymerizable resin having a high molecular weight obtained from a chain extender, and a diluent. The effect is that the tack-free property is certainly improved, but when the polyhydric phenol or polyfunctional isocyanate described therein is used as a chain extender, the viscosity increases with the increase in the molecular weight and the workability increases. However, there was room for improvement because it decreased.

Further, the required characteristics for the printed circuit board are still known, and one of them is required to have a low dielectric constant in order to improve the signal propagation speed. However, a polar group such as a hydroxyl group or a urethane bond is present in the composition obtained by the above publication, and it has been difficult to reduce the dielectric constant. That is, there is room for improvement in improving the electrical characteristics such as lowering the dielectric constant at the same time as improving the tack-free property after pre-drying by increasing the molecular weight of the photopolymerizable resin.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and improves the tack-free property of a pre-dried coating film, and makes it possible to improve the electrical characteristics by lowering the dielectric constant. The purpose of the present invention is to provide a photosensitive resin composition for image formation.

[0008]

Means for Solving the Problems As a result of various investigations by the present inventors on a photosensitive resin composition for image formation, an image was formed using a curable resin having two or more radically polymerizable unsaturated bonds in one molecule. Focusing on the fact that when a photosensitive resin composition for forming is constituted, a cured product having excellent properties can be formed, and two or more radical polymerizable unsaturated bonds and one or more hydroxyl groups and A curable resin having a carboxyl group and / or a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, and a photopolymerization initiator,
When a coating film is formed from the photosensitive resin composition for image formation, these react with each other, and the hydroxyl group and / or the carboxyl group reacts with the vinyl ether group and / or the vinyl thioether group, so that 2 in one molecule. A compound having more than one vinyl ether group and / or vinyl thioether group serves as a chain extender to increase the molecular weight of the curable resin, improving the tack-free property of the pre-dried coating film and consuming hydroxyl and carboxyl groups. As a result, it has become possible to reduce the dielectric constant, and it has been found that these characteristics can be satisfied at a high level in a well-balanced manner, and it has been conceived that the above problems can be solved satisfactorily. For example, when the photosensitive resin composition for image formation contains a solvent, a tack-free property is exhibited by coating on a substrate and causing a chain extension reaction while volatilizing the solvent component during preliminary drying. . Further, when a curable resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an unsaturated monobasic acid is used, the physical properties of the cured product are further improved, and A curable resin having a carboxyl group introduced therein, that is, a resin obtained by reacting a polybasic acid anhydride, exhibits excellent alkali developability, thereby providing a photosensitive resin composition for image formation. The inventors have found that the basic performance of (1) can be exhibited more sufficiently, and have reached the present invention.

That is, the present invention is a curable resin having two or more radically polymerizable unsaturated bonds and one or more hydroxyl group and / or carboxyl group in one molecule, and two or more vinyl ethers in one molecule. A photosensitive resin composition for image formation containing a compound having a group and / or a vinyl thioether group, and a photopolymerization initiator. The present invention is described in detail below.

In the photosensitive resin composition for image formation of the present invention, as a curable resin having two or more radically polymerizable unsaturated bonds and one or more hydroxyl group and / or carboxyl group in one molecule, One kind or two or more kinds can be used, but a vinyl obtained by reacting an unsaturated monobasic acid with an epoxy resin having two or more epoxy groups in one molecule in terms of excellent physical properties of a cured product. Preference is given to using esters. In this case, by reacting the unsaturated monobasic acid with the epoxy group in the epoxy resin, a vinyl ester having a radical-polymerizable unsaturated double bond introduced into the resin can be obtained.

The epoxy resin as the starting material for the vinyl ester is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used. Resin; Biphenyl type epoxy resin; Alicyclic epoxy resin;
Polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl etherethane; phenol novolac type epoxy resins and cresol novolac type epoxy resins; phenol, o-cresol, m-
Reaction products of polyphenol compounds obtained by condensation reaction of phenol compounds such as cresol and naphthol with aromatic aldehydes having a phenolic hydroxyl group and epichlorohydrin; phenol compounds and diolefin compounds such as divinylbenzene and dicyclopentadiene Reaction product of a polyphenol compound obtained by the addition reaction with epichlorohydrin; a ring-opening polymerization product of 4-vinylcyclohexene-1-oxide epoxidized with peracid; an epoxy resin having a heterocycle such as triglycidyl isocyanurate A phenol aralkyl type epoxy resin; and the like. In addition, two or more molecules of these epoxy resins may be chain-extended by binding by a reaction with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound or a polyvalent thiol.
These can use 1 type (s) or 2 or more types.

The unsaturated monobasic acid is a monobasic acid having one carboxyl group and one or more polymerizable unsaturated bonds. Specific examples include acrylic acid, methacrylic acid,
Crotonic acid, cinnamic acid, β-acryloxypropionic acid, a reaction product of a hydroxyalkyl (meth) acrylate having one hydroxyl group and one (meth) acryloyl group with a dibasic acid anhydride, and one hydroxyl group Group and a reaction product of a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups with a dibasic acid anhydride, and specific preferred examples thereof include (meth) acryloyl such as acrylic acid and methacrylic acid. It has a group. These can use 1 type (s) or 2 or more types.

In the reaction of the above-mentioned epoxy resin and unsaturated monobasic acid, the amount of unsaturated monobasic acid used is 0.8-1. To 1 chemical equivalent of one epoxy group in the epoxy resin.
It is suitable to be 1 mol, in the presence or absence of a radical polymerizable monomer or a diluent such as a solvent described later, in the presence or absence of a polymerization inhibitor such as hydroquinone and oxygen, and a tertiary amine such as triethylamine, triethylbenzyl. Quaternary ammonium salt such as ammonium chloride, 2-ethyl-4-
Two compounds per molecule, usually at 80 to 130 ° C, in the presence of an imidazole compound such as methylimidazole, a phosphorus compound such as triphenylphosphine, a reaction catalyst such as an organic acid or inorganic salt of a metal, or a chelate compound. A curable resin having the above radically polymerizable unsaturated bond and an alcoholic hydroxyl group formed by ring opening of an epoxy group can be obtained.

In the reaction between the above epoxy resin and unsaturated monobasic acid, a phenol compound having a long-chain alkyl group, a substituent containing an aromatic ring, an alcoholic hydroxyl group, etc., is used in combination with the unsaturated monobasic acid. Or acetic acid, propionic acid,
One kind or two or more kinds of monobasic acids having no radical polymerizability such as dimethylolpropionic acid may be used. The kind and the amount of these are appropriately selected according to required properties such as physical properties of the cured product. When these are used in combination with an unsaturated monobasic acid to obtain a curable resin, one of the epoxy groups in the epoxy resin
It is suitable that the unsaturated monobasic acid is 0.4 mol or more, preferably 0.5 or more with respect to the chemical equivalent, and the unsaturated monobasic acid and the phenol compound or the monobasic acid having no radical polymerizability. Is preferably 0.8 to 1.1 mol per 1 chemical equivalent of the epoxy group. If the amount of unsaturated monobasic acid is small, the radical polymerizability becomes insufficient. On the other hand, if the total amount exceeds 1.1 mol, unreacted residual unsaturated monobasic acid and the like increase, and these low molecular weight compounds cause deterioration of the properties of the cured product, which is not preferable. From the above, as the curable resin in the present invention,
A vinyl ester having a radically polymerizable unsaturated bond and a hydroxyl group is obtained.

In the present invention, since alkali development is also possible, a polybasic acid is added to a curable resin having two or more radically polymerizable unsaturated bonds and one or more hydroxyl groups in one molecule. A product obtained by reacting an anhydride can be used. For example, the above-mentioned curable resin has an alcoholic hydroxyl group formed by ring-opening of the epoxy group during the reaction between the unsaturated monobasic acid and the epoxy group in the epoxy resin. In the present invention, a carboxyl group can be introduced into a vinyl ester by reacting this hydroxyl group with a polybasic acid anhydride, and the obtained vinyl ester can be alkali-developed. Such an epoxy resin having two or more epoxy groups in one molecule, an unsaturated monobasic acid, and a polybasic acid anhydride are reacted with each other to obtain two or more epoxy resins in one molecule. Use as a curable resin having a radically polymerizable unsaturated bond and one or more hydroxyl groups and / or carboxyl groups is one of the preferred embodiments of the present invention.

Examples of the polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride,
Pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride,
Dibasic acid anhydrides such as reaction products of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic anhydride or maleic anhydride; trimellitic acid; biphenyltetracarboxylic dianhydride , Naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride,
Examples thereof include aliphatic or aromatic tetrabasic acid dianhydrides such as pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride, and one or more of them can be used.

In the reaction between the polybasic acid anhydride and the vinyl ester, the amount of the polybasic acid anhydride used is 0.
1 to 1.1 mol is suitable, and it is preferable that the acid value is 30 mgKOH / g or more in order to exhibit good alkali developability.

The above-mentioned reaction for introducing a carboxyl group is usually carried out at 50 to 130 ° C. in the presence or absence of a diluent such as a solvent or a radical-polymerizable monomer described later, if necessary, in the presence of a polymerization inhibitor such as hydroquinone or oxygen. To do. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine is used as a catalyst. You may add.

As described above, the curable resin having two or more radical polymerizable unsaturated bonds and one or more hydroxyl group and / or carboxyl group in one molecule is a radical polymerizable unsaturated bond and an alcoholic hydroxyl group. A vinyl ester having and, or an alkali developable vinyl ester also having a carboxyl group is obtained.

The compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule in the present invention is not particularly limited, and may be a monomer or an oligomer,
It may be a polymer, and one kind or two or more kinds may be used. Examples of such compounds include the compounds described in the following (1) to (6). In addition, having two or more vinyl ether groups and / or vinyl thioether groups in one molecule means that the total number of vinyl ether groups and vinyl thioether groups present in one molecule is two or more.

(1) Ethylene glycol divinyl ether, propylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, butanediol diisopropenyl ether, pentanediol divinyl ether, hexane Low-molecular-weight polyvalent vinyl ethers such as diol divinyl ether, neopentyl glycol diisopropenyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and acetic acid diisocyanate ester.

(2) An adduct of a low molecular weight polyvalent vinyl ether and a polyol, such as the low molecular weight polyvalent vinyl ether of (1) above, ethanediol, propanediol,
Butanediol, pentanediol, octanediol or their homologues or corresponding oligomeric ethers, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, polyvinyl alcohol, bisphenol A, resorcin, hydroquinone. Alternatively, adducts thereof with polyols such as derivatives thereof, trishydroxyethyl isocyanurate, hydroxyl group-containing epoxides, hydroxyl group-containing polyethers, hydroxyl group-containing polyesters and hydroxyl group-containing polyacrylics.

(3) An adduct of a low molecular weight polyvalent vinyl ether and a polyvalent carboxylic acid, for example, the low molecular weight polyvalent vinyl ether of (1) above, and oxalic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid, azelaic acid, sebacic acid,
Polycarboxylic acid such as decamethylene dicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylated hexahydrophthalic acid, trimellitic acid and pyromellitic acid An adduct with a polyester resin or acrylic resin having two or more carboxyl groups.

(4) Reaction products of monovinyl ether or acetal with polyol, for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and the like. Aliphatic vinyl thioether compounds corresponding to these, further 2,3-dihydrofuran, 3,4-dihydrofuran,
2,3-dihydro-2H-pyran, 3,4-dihydro-
2H-pyran, 3,4-dihydro-2-methoxy-2H
-Pyran, 3,4-dihydro-4,4-dimethyl-2H
-Pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2
-A new vinyl ether from an acetal compound obtained by reacting a cyclic vinyl ether compound such as sodium carboxylate and a corresponding monovinyl ether or monovinyl thioether such as a cyclic vinyl thioether compound with the polyols exemplified in (2) above. Cleaved compound.

(5) An adduct of a hydroxyl group-containing monovinyl ether and a polyvalent isocyanate compound, for example, ethylene glycol monovinyl ether, propylene glycol monovinyl ether, 1,4-butylene glycol monovinyl ether, methanol dihydropyran, and tetramethylene diisocyanate. , Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, isophorone diisocyanate, perhydro-2,4'- or -4, 4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, diphenyl methene Down-2,4'-or 4,4'
Diisocyanate, 3,2- or 3,4-diisocyanate-4'-methyldiphenylmethane, naphthalene-
1,5-diisocyanate, triphenylmethane-4,
Addition products of 4 ', 4 "-triisocyanate or these low molecular weight polyvalent isocyanates with isocyanurate type, buret type and polyol addition type polyisocyanates. (6) α, β-unsaturated carboxylic acid ester homopolymer Alternatively, a transesterification reaction product of a copolymer and a vinyl ether group-containing alcohol or thiol.

As for the amount of the compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, the preferable lower limit is 0.5 part by weight, and the more preferable lower limit is 1 with respect to 100 parts by weight of the curable resin. Parts by weight. The preferred upper limit is 70 parts by weight, and the more preferred upper limit is 50 parts by weight. If it is less than 0.5 part by weight, sufficient tack-free property may not be obtained after heating and drying, and if it exceeds 70 parts by weight, the molecular weight becomes too large at the time of heating and drying, which causes deterioration of developability. Therefore, there is a possibility that an image as the pattern film cannot be formed. Further, the hydroxyl group of the curable resin and /
Alternatively, the preferable lower limit of the vinyl ether group and / or the vinyl thioether group is 0.0 with respect to 1 mol of the carboxyl group.
2 mol, and a more preferable lower limit is 0.04 mol. The preferable upper limit is 0.9 mol, and the more preferable upper limit is 0.7 mol.

The photosensitive resin composition for image formation of the present invention comprises
Although it contains a photopolymerization initiator, known photopolymerization initiators can be used, and specifically, benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and alkyl ethers thereof;
Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-
Acetophenones such as (1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone , 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 Benzophenones such as', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1
-One and 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1; acylphosphine oxides, xanthones and the like.

The above photopolymerization initiators are used as one kind or as a mixture of two or more kinds, and the photosensitive resin composition 10 for image formation is used.
It is preferable that 0.5 to 30 parts by weight is contained with respect to 0 parts by weight. When the amount of the photopolymerization initiator is less than 0.5 parts by weight, the light irradiation time must be increased or the polymerization is difficult to occur even if the light irradiation is performed, so that an appropriate surface hardness can be obtained. It may run out. Further, even if the amount of the photopolymerization initiator exceeds 30 parts by weight, there is no merit of using a large amount. Further, the photopolymerization initiator is used in an amount of 1 to 300 parts by weight based on 100 parts by weight of the curable resin and a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule. It is more preferable to use 2 to 150 parts by weight.

The photosensitive resin composition for image formation of the present invention comprises
Further, it preferably contains a catalyst, and an acid is suitable as the catalyst. The acid is not particularly limited and includes, for example, formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, glycolic acid and other aliphatic monocarboxylic acids; oxalic acid, maleic acid,
Aliphatic polycarboxylic acids such as oxaloacetic acid, malonic acid, fumaric acid, tartaric acid and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; benzenesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid Salts, aromatic sulfonic acids such as quinolinium p-toluenesulfonic acid or salts thereof; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; sodium hydrogen sulfate, hydrogen sulfate Hydrogen sulfate such as potassium; mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid and polyphosphoric acid; and heteropolyacids such as phosphovanadomolybdic acid, phosphotungstomolybdic acid and keitangustmolybdic acid. These may be used alone or in combination of two or more.

The amount of the catalyst used may be appropriately set depending on the type and combination of the curable resin used in the present invention and the compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule. But,
From the viewpoint of yield, stability of catalyst, productivity and economic efficiency, for example, 0.0005 to 1 with respect to 100 parts by weight of the curable resin.
It is preferable to use parts by weight. More preferably 0.0
It is from 01 to 0.5 parts by weight.

In the present invention, a chain extender other than a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, that is, a group having reactivity with a functional group of a curable resin is used. A compound having two or more molecules in the molecule is used in combination with the compound having a vinyl ether group and / or a vinyl thioether group to increase the molecular weight of the curable resin when forming a coating film from the photosensitive resin composition for image formation. Good. Examples of other chain extenders include isocyanate compounds and tetrabasic acid dianhydrides for hydroxyl groups, and epoxy resins and oxazoline compounds for carboxyl groups.

Further, a curable resin obtained by reacting a (meth) acrylic monomer containing an isocyanate group, an epoxy group or a vinyl (thio) ether group is used, or in a photosensitive resin composition for image formation, such a ( By including a (meth) acrylic monomer, it is possible to increase the number of unsaturated double bonds in the curable resin.
Further, the photosensitive resin composition for image formation contains a monofunctional vinyl ether having no unsaturated double bond or a monofunctional vinyl thioether in combination with a compound having two or more vinyl ether groups and / or a vinyl thioether group. May be.

The photosensitive resin composition for image formation of the present invention comprises
The above-mentioned curable resin, a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, and a photopolymerization initiator as essential components, but if necessary, other components such as a diluent. May be included.

The image forming photosensitive resin composition of the present invention may contain a radically polymerizable compound capable of participating in a photopolymerization reaction. The radical polymerizable compound includes an oligomer and a monomer. As the radically polymerizable oligomer, unsaturated polyester, urethane acrylate, polyester acrylate, etc. can be used, and as the radically polymerizable monomer, those described below can be used. Aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallylphthalate and diallylbenzenephosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate,
(2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth)
(Meth) acrylic monomers such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; Triallyl cyanurate and the like can be mentioned. These can be used alone or in combination of two or more,
5 to 500 parts by weight should be added to 100 parts by weight of the above curable resin and a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, depending on the intended use and required physical properties. Is preferred.

The photosensitive resin composition for image formation of the present invention comprises
It is suitable for image formation and fine processing, and curing by irradiation with light is recommended, but it is also possible to add a known thermal polymerization initiator to perform thermal curing. In that case, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, fillers, thickeners, pigments and other known additives are used depending on the application. You may. Further, various reinforcing fibers can be used as reinforcing fibers to form a fiber-reinforced composite material.

The photosensitive resin composition of the present invention is used to form an image,
When used as a liquid photosensitive resin composition for coating on a substrate and irradiating with light to obtain a cured coating film, a solvent may be added to the composition from the viewpoint of workability and the like. As the solvent, hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid. (J)
Examples thereof include esters such as methyl, (di) methyl succinate, and (di) methyl adipate; ketones such as methyl isobutyl ketone and methyl ethyl ketone; ethers such as (di) ethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more, and are used in an appropriate amount so as to obtain an optimum viscosity during the coating operation.

The photosensitive resin composition for image formation of the present invention comprises
It is preferably used as a photosensitive resin composition for image formation and fine processing. In that case, in addition to the curable resin described above, a compound having two or more vinyl ether groups and / or vinyl thioether groups in one molecule, and an essential component of the photopolymerization initiator, it is optionally used. In addition to the above diluents, radically polymerizable unsaturated monomers and solvents, talc, clay, fillers such as barium sulfate,
Coloring pigments, defoamers, coupling agents, leveling agents, etc., novolac type epoxy resins, bisphenol type epoxy resins, cycloaliphatic epoxy resins, epoxy resins such as triglycidyl isocyanate, and epoxy curing agents such as dicyandiamide and imidazole compounds. Etc. can also be added.

In the photosensitive resin composition for image formation of the present invention, when a curable resin having no carboxyl group introduced is used, it is not applied after being applied to a substrate and exposed to obtain a cured coating film. The exposed portion can be solvent-developed using the above-mentioned solvent or a halogen-based solvent such as trichloroethylene.

When a curable resin having a carboxyl group introduced is used, the unexposed portion is dissolved in an aqueous alkali solution, so that alkaline development can be carried out. Examples of usable alkalis include alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine , Diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethylmethacrylate, polyethyleneimine, and other water-soluble organic amines. Two or more kinds can be mixed and used.

The photosensitive resin composition for image formation of the present invention comprises
In addition to the method of directly applying it to the substrate in a liquid state, it may be used in the form of a dry film (which may be laminated with a protective film) which is previously applied to a film such as polyethylene terephthalate and dried. In this case, a dry film may be laminated on the substrate and the film may be peeled off before or after exposure.

Further, as used in printing plate making,
A method of scanning and exposing a laser beam directly on a coating film by using digitized data without using a pattern forming film at the time of exposure (CTP, Computer)
To Plate) can also be adopted.

The photosensitive resin composition for image formation of the present invention comprises
For example, a solder resist for manufacturing a printed wiring board, an etching resist, an electroless plating resist, an insulating layer of a build-up method printed wiring board, a black matrix for manufacturing a liquid crystal display board, a color filter, a photo spacer, an electrode, a partition wall, a phosphor, It can be suitably applied to various uses such as printing plate making.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is
It means "parts by weight".

Synthesis Example 1 Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name "Epototo YD-127", epoxy equivalent 184) was placed in a reactor equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer. 368 parts, acrylic acid 146.8 parts, propylene glycol monomethyl ether acetate 277 parts,
Triphenylphosphine 2.6 as esterification catalyst
Part, and methylhydroquinone 0.6 as a polymerization inhibitor
A portion was charged and reacted at 115 ° C. while introducing air to obtain a mixture (resin mixture 1) with propylene glycol monomethyl ether acetate containing 65% of a curable resin having an acid value of 8 mgKOH / g.

Synthesis Example 2 To 400 parts of the resin mixture 1 obtained in Synthesis Example 1, 137.7 parts of tetrahydrophthalic anhydride and 74.1 parts of propylene glycol monomethyl ether acetate were added to give 10 parts.
The mixture was reacted at 0 ° C. to obtain a mixture (resin mixture 2) with propylene glycol monomethyl ether acetate containing 65% of a curable resin having an acid value of 135 mgKOH / g.

Synthesis Example 3 A cresol novolac type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name "Epototo Y" was placed in the same reactor as in Synthesis Example 1 above.
DCN-703 ", epoxy equivalent 201.5) 403 parts, acrylic acid 146.9 parts, propylene glycol monomethyl ether acetate 296.1 parts, triphenylphosphine 2.7 parts as an esterification catalyst, and a polymerization inhibitor. Charge 0.4 parts of methylhydroquinone, react at 115 ° C while introducing air, acid value 9m
A mixture (resin mixture 3) with propylene glycol monomethyl ether acetate containing 65% of gKOH / g curable resin was obtained.

Synthesis Example 4 To 400 parts of the resin mixture 3 obtained in Synthesis Example 3, 71.6 parts of tetrahydrophthalic anhydride and 38.5 parts of propylene glycol monomethyl ether acetate were added to obtain 100 parts.
The mixture was reacted at 0 ° C. to obtain a mixture (resin mixture 4) with propylene glycol monomethyl ether acetate containing 65% of a curable resin having an acid value of 88 mgKOH / g.

Synthesis Example 5 A cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name "EOCN-1" was placed in the same reactor as in Synthesis Example 1 above.
03S ", epoxy equivalent 218) 218 parts, acrylic acid 73.4 parts, propylene glycol monomethyl ether acetate 156.9 parts, triphenylphosphine 1.5 parts as an esterification catalyst, and methylhydroquinone 0. Two parts were charged and reacted at 115 ° C. while introducing air to obtain a mixture with propylene glycol monomethyl ether acetate containing 65% of a curable resin having an acid value of 8 mgKOH / g. Next, 92.9 parts of tetrahydrophthalic anhydride and 50 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 100 ° C.
And the curable resin with an acid value of 96 mgKOH / g
A mixture with propylene glycol monomethyl ether acetate containing 5% was obtained. Furthermore, 7.4 parts of bisphenol A type epoxy resin (“Epotote YD-127”, epoxy equivalent 184) and 4 parts of propylene glycol monomethyl ether acetate were added and reacted at 115 ° C. to extend the chain with an acid value of 89 mgKOH / g. A mixture (resin mixture 5) with propylene glycol monomethyl ether acetate containing 65% of the curable resin was obtained.

Examples 1 to 5 and Comparative Examples 1 to 4 Using the obtained solutions, according to the blending composition shown in Table 1,
A photosensitive resin composition was prepared and evaluated by the following methods. The results are shown in Table 2.

[0050]

[Table 1]

[Tack-Free Property] Each photosensitive resin composition was applied on a copper plate to a thickness of 20 to 30 μm, and dried at 80 ° C. for 30 minutes in a hot air circulation type drying oven to obtain a coating film. It was evaluated by touching with the finger. When no tack was observed at all, it was evaluated as ○, when slightly tack was recognized as Δ, and when significant tack was recognized as ×.

[Developability-1] A dry coating film was formed in the same manner as in the evaluation of tack-free property. Then, using propylene glycol monomethyl ether acetate,
Development is carried out at 30 ° C. for 60 seconds under a pressure of 0.21 MPa, and the presence of the remaining coating film is visually evaluated. One that has been completely developed is ◯, one that slightly retains Δ, and adhesion is Many things that remained are marked with x.

[Developability-2] When evaluating tack-free property
A dry coating film was formed in the same manner as in. Then 1% Na _Two
CO_Three30 with an aqueous solution under a pressure of 0.21 MPa
Develop at 60 ° C for 60 seconds and visually check for the presence of residual coating.
Then, the same criteria as the developability-1 were evaluated.

[Exposure Sensitivity] A dry coating film was formed in the same manner as in the tack-free property evaluation. Then stofer 2
A 1-step step tablet was brought into close contact with the coating film and irradiated with a light amount of 500 mJ / cm ² by a 1 kW ultra-high pressure mercury lamp. Development was performed under the same conditions as in the evaluation of developability, and the number of remaining step tablets was examined.

[Coating Film Hardness] A dry coating film was formed in the same manner as in the tack-free property evaluation, and the coating film was cured by irradiating it with a light amount of 500 mJ / cm ² using an ultrahigh pressure mercury lamp of 1 kW. Then, after heating at 150 ° C for 30 minutes, JIS K
The test was carried out according to the test method of -5400, and evaluation was made by using the pencil hardness tester with the highest hardness that does not scratch the coating when a load of 1 kg is applied.

[0056]

[Table 2]

[0057]

The photosensitive resin composition for image formation of the present invention has the above-mentioned constitution and improves the tack-free property of the pre-dried coating film, and it is possible to improve the electric characteristics by lowering the dielectric constant. The printed wiring board manufacturing solder resist, etching resist, electroless plating resist, build-up method printed wiring board insulating layer, liquid crystal display board manufacturing black matrix, color filter,
It can be suitably applied to various uses such as a photo spacer, an electrode, a partition, a phosphor, and a printing plate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/28 H05K 3/28 D 3/46 3/46 TF term (reference) 2H025 AA15 AA16 AA20 AB15 AB17 AC01 AD01 BC13 BC23 BC24 BC42 BC74 BC85 BC86 CA00 CC17 EA10 5E314 AA27 AA32 DD07 GG24 5E339 BC02 CC01 5E343 AA22 CC62 DD32 GG03 5E346 AA12 CC09 EE31 HH11

Claims (3)

[Claims] 1. A curable resin having two or more radical polymerizable unsaturated bonds and one or more hydroxyl groups and / or carboxyl groups in one molecule, and two or more vinyl ether groups in one molecule and / Alternatively, a photosensitive resin composition for image formation comprising a compound having a vinyl thioether group and a photopolymerization initiator. 2. The curable resin is obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an unsaturated monobasic acid. The image forming photosensitive resin composition. 3. The curable resin is an epoxy resin having two or more epoxy groups in one molecule, an unsaturated monobasic acid,
The photosensitive resin composition for image formation according to claim 1, which is obtained by reacting a polybasic acid anhydride.