JPS62277422A - Photo-sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing specific epoxidized resin, modified resin, epoxy compound, thermal reaction catalyst and photo-polymerization initiator at specific ratios, having high sensitivity and resolution to actinic light and giving a coating film to which a mask film can be directly and closely applied. CONSTITUTION:The objective composition contains (A) 5-60(wt)%, preferably 10-40% epoxidized resin produced by reacting a phenolic compound having halogen atom and/or alkyl group with an aldehyde compound and epoxidizing the resultant novolac resin, (B) 20-75%, preferably 25-60% modified resin produced by reacting the resin A with an unsaturated carboxylic acid [e.g. (meth)acrylic acid], (C) 0.01-45%, preferably 0.02-30% epoxy compound (excluding the components A and B), (D) 0.01-10% thermal reaction catalyst enabling the thermal reaction of epoxy group and (E) 0.001-15% photo-polymerization initiator enabling the photo-polymerization of unsaturated group.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photosensitive resin composition, more specifically, it has high sensitivity to actinic rays and high resolution, and is heat-drying after application. This makes it possible to expose the mask film directly to the surface of the coating film, and further improves the electrical insulation properties of the cured film.
The present invention relates to a photosensitive resin composition suitable for a resist for printed circuit boards, which has excellent mechanical properties, adhesion to a substrate, and soldering heat resistance, and can be developed with a nonflammable solvent.

(Prior Art) Photosensitive resin compositions are used as materials for printed circuit boards that meet the recent demands for higher density and multilayer packaging, and film-like photosensitive resin compositions have been developed.

However, the film-like photosensitive resin composition has a limited resolution because of its film form, and has insufficient adhesion to printed circuit boards, and is not preferable for automated production of printed circuit boards.

On the other hand, liquid photosensitive resin compositions are known as those that meet more advanced requirements, and there are two major types of these resin compositions: acrylic photosensitive resin compositions and epoxy photosensitive resin compositions. Separated.

Acrylic photosensitive resin compositions consist mostly of photocurable acrylic or methacrylic monomers, oligomers, or polymers.

The above-mentioned acrylic photosensitive resin composition has a drawback of poor electrical insulation retention under wet conditions.

Furthermore, as a liquid photosensitive resin composition, a composition is known in which a photodegradable epoxy curing catalyst is mixed, which is decomposed by actinic light to generate reactive species, in order to impart photosensitivity to the epoxy resin oligomer. However, since the photodegradable epoxy curing catalyst is an acidic compound, it has the disadvantage of poor electrical insulation retention under wet conditions, similar to acrylic photosensitive resin compositions.

(Problem to be solved by the invention) However, since the electrical insulation properties of epoxy resin itself are generally better than those of acrylic resin, it is possible to make use of the high electrical insulation properties of epoxy resin itself, and to use printed circuits. The photosensitive resin composition for substrates has the required adhesion to the substrate, soldering heat resistance, electrical insulation properties, and mechanical properties. It is possible to expose the mask film directly to the film surface, and it also uses non-flammable solvents commonly used in the conventional printed circuit board industry (
For example 1. L L-trichloroethane (chlorocene)
) It is desired to develop an epoxy-based photosensitive resin composition that can be developed.

(Means for Solving the Problems) The present invention is produced by epoxidizing a novolak resin obtained by reacting (A) a phenol having at least one kind selected from a halogen atom and an alkyl group with an aldehyde compound. (B) 20 to 75% by weight of a modified resin obtained by reacting the epoxidized resin of (A) with an unsaturated carboxylic acid; (C) at least one epoxy compound; (However, excluding the above components A and B) 0.01 to 45% by weight, (D) 0.0 of a thermal reaction catalyst capable of thermally reacting an epoxy group
1 to 10% by weight, and (E) 0.001 to 15% by weight of a photopolymerizable initiator capable of photopolymerizing unsaturated groups.
The present invention relates to a photosensitive resin composition containing the following.

Examples of the halogen-containing phenols in component (A) of the photosensitive resin composition of the present invention include o-chlorophenol, m-ditetraphenol, p-chlorophenol, o-7'lomophenol, m-bromophenol, and m-chlorophenol. phenol, p
- Bromophenol, 4-bromo-2-chlorophenol, etc., as phenols having an alkyl group, 0
-cresol, m-cresol, p-cresol, 2.
5-xylenol, 2,4-xylenol, 2,5-
Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3゜5-trimethylphenol, 2,3.6-trimethylphenol, 2
, 4.6-) dimethylphenol, 0-ethylphenol, m-ethylphenol, p-ethylphenol, 2
-Methylresorcinol, 5-methylresorcinol, and the like. Furthermore, as phenols having a halogen atom and an alkyl group, 4-chloro-
〇-cresol, 6-chloro-〇-cresol, 4-chloro-m-cresol, 6-chloro-m-cresol,
4-chloro-3,5-dimethylphenol, 2-chloro-4,5-dimethylphenol, 4-chloro-3,5-
Xylenol, 4-bromo-0-cresol, 6-bromo-0-cresol, 4-bromo-m-cresol, 6
Examples of the aldehyde compound in component (A) include -bromo-m-cresol, 4-bromo-2,6-dimethylphenol, and 4-bromo-3,5-dimethylphenol.
Formaldehyde, acetaldehyde, propionaldehyde, n-butyl-aldehyde, benzaldehyde,
Examples include phenylacetaldehyde, furfural, acrolein, and crotonaldehyde.

When synthesizing the novolac resin, the amount of aldehyde compound used is preferably 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol having at least one selected from halogen atoms and alkyl groups. used. If it is less than 0.7 mol, the remaining amount of unreacted phenols will increase, so the softening point of the novolak resin will be low, and if it exceeds 3 mol, the novolak resin will gel (there is a positive tendency).

In the synthesis of novolac resins, phenols and aldehyde compounds are usually polycondensed using an acid catalyst. The acid catalyst includes inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid;
Alternatively, organic acids such as formic acid, oxalic acid, and acetic acid may be mentioned.

The amount of these acid catalysts used is usually 1 x 10-7 to 5 x 10-1 mol, preferably 1 x 10-1 mol, per mol of phenol.
101 to 5XIO-1 mole.

In the synthesis of novolak resin, it is not necessary to use a reaction medium, but water or a hydrophilic solvent, or a mixture of these can also be used as the reaction medium. Hydrophilic solvents used in this case include, for example, alcohols such as methanol, ethanol, propatool, butanol, ethers such as tetrahydrofuran, dioxane, diclime, esters such as ethyl acetate, propyl acetate, butyl acetate, or acetonitrile. propionitrile,
Nitriles such as butyronitrile are mentioned. The amount of these reaction media used is usually 5,000 parts by weight or less, preferably 10 to 1,000 parts by weight per 100 parts by weight of phenol.
Parts by weight. The reaction temperature is appropriately selected depending on the reaction raw materials, but is usually 10 to 200°C, preferably 60 to 200°C.
It is 160°C.

When epoxidizing the novolak resin, the novolak resin is reacted with epihalohydrin.

Examples of the shrimp halohydrin here include epichlorohydrin and epibromohydrin.

Epoxidized novolac resin usually contains novolac resin and 0.005 to 3 molar equivalents of shrimp halohydrin per 1 molar equivalent of phenolic hydroxyl group in the novolak resin.
It is synthesized by uniformly dissolving it in a solvent or without a solvent, and adding 1 to 3 molar equivalents of an alkaline catalyst to 1 molar equivalent of phenolic hydroxyl group to cause a reaction. The alkaline catalyst is 5 to 60% by weight, preferably 20 to 50% by weight of an inorganic alkali such as sodium hydroxide or potassium hydroxide.
Aqueous solutions of pyridine and organic amines such as triethylamine are used. As the solvent, a solvent that dissolves the novolak resin, such as acetone, dimethylformamide, and tetrahydrofuran, can be used.

The reaction temperature is usually 20-200°C, preferably 50-200°C.
The temperature is 120°C.

In addition, the epoxidized resin of component (A) is commercially available,
For example, Japanese leaf juice! ! EOCN-102, EOCN-1
03, EOCN-104, EOCN-1020, etc.

The amount of component (A) used is 5 to 60% by weight, preferably 1
It is 0 to 40% by weight. The amount of component (A) used is 5% by weight.
If it is less than 60% by weight, a surface with sufficient hardness cannot be obtained.
If it is more than that, the sensitivity of the photosensitive resin composition decreases.

Component B is produced by reacting the epoxidized resin (A) with an unsaturated carboxylic acid in an organic solvent.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, allyl acetic acid, phthalic acid monoacrylate, phthalic acid monomethacrylate, terephthalic acid monoacrylate, terephthalic acid monomethacrylate, and phthalic acid monoacrylate. Acid mono (β-
Acryloyloxyethyl) ester, monophthalate
(β-methacryloyloxyethyl) ester, terephthalic acid mono (β-acryloyloxyethyl) ester, terephthalic acid mono (β-methacryloyloxyethyl) ester, succinic acid mono (β-acryloyloxyethyl) ester, succinic acid mono (β-acryloyloxyethyl) ester, -methacryloyloxyethyl) ester, maleic acid mono(β
- Acryloyloxyethyl) ester, maleic acid mono (β-methacryloyloxyethyl) ester, fumaric acid, straconic acid, mesaconic acid with 1 or more carbon atoms
12 alkyl, alkenyl, allyl monoesters, etc.

The amount of unsaturated carboxylic acid used is 0.1 to 1 mol, preferably 0.2 to 0.6 mol, per equivalent of epoxy group in the epoxy resin used.

Examples of the organic solvent used in the synthesis of component (B) include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. used.

The amount of these organic solvents to be used is determined when the solid content concentration of the reaction solution is 5.
The amount is 90% by weight, preferably 30-70% by weight.

In the synthesis of component (B), a reaction catalyst can be used, such as triethylamine, pyridine, lutidine,
Organic amines such as collidine are used. The amount of these catalysts used is preferably 0.001 to 10 mol%, particularly preferably 0.05 to 5 mol%, based on 1 mol of unsaturated carboxylic acid used in the reaction.

The reaction temperature in the synthesis of component (B) is not particularly limited, but is usually 0 to 200°C, preferably 20 to 80°C.

Component (B), which is a reaction product obtained in this way, can be isolated and purified by precipitating the product in a specific solvent. Examples of the solvent used in this case include methanol, ethanol, etc. Examples include alcohols such as, ethers such as diethyl ether, and hydrocarbon solvents such as heptane, hexane, and cyclohexane.

When component (B) is used as a component of the photosensitive resin composition of the present invention, the resulting reaction solution is used as it is, or the reaction product is isolated and purified as described above.

The amount of component (B) used in the photosensitive resin composition of the present invention is 20 to 75% by weight, preferably 25 to 60% by weight. If the amount of component (B) used is less than 20%, staining occurs even if the photosensitive resin composition is applied onto a substrate and then dried by heating, and the mask film cannot be exposed in close contact. 75 again
If it exceeds % by weight, the adhesion of the photosensitive resin composition to the substrate after photocuring will be insufficient, and the coating film will become brittle, making it impractical.

The epoxy compound used in the present invention (excluding components A and B) (component (C)) has the general formula (where n is O or an integer from 1 to 20, and X is -CH2-1
'-C(CH3)2 or )S02, Y is a hydrogen atom, C
H3 or a halogen atom such as a bromine atom or a chlorine atom) can be exemplified, and specifically, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether,
Bisphenol S diglycidyl ether (X=SO2)
, an epoxy oligo synthesized from bisphenol A etc. and diglycidyl ether? -(X=C(CH3)2 and n-1 to 20), etc. can be mentioned. Also, monoepoxy ethers such as glycidyl methacrylate, allyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, monoepoxy esters such as benzoic acid glycidyl ester, sorbic acid glycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Gepoxy compounds such as polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dibromneopentyl glycol diglycidyl ether, phthalic acid diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, dicrycerol polyglycidyl ether, 2 such as polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, triglycidyl isocyanurate, 1.3-(N,N-diglycidylaminomethyl)benzene, 1.3-(N,N-diglycidylaminomethyl)cyclohexane, etc. A polyepoxy compound having three or more epoxy groups or Epicoat manufactured by Yuka Shell Epoxy Co., Ltd. can be used.

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

The amount of component (C) to be blended is appropriately selected depending on the solubility of component (C) in the developer, and is 0.01 to 45% by weight, preferably 0.2 to 30% by weight. This amount is 0.01
If the percentage by weight is ungrooved, the adhesion of the photosensitive resin composition to the substrate will decrease, while if it exceeds 45% by weight, the sensitivity to actinic rays and 1,1,1-trichloroethane, which is a nonflammable solvent, will decrease. (Chlorocene) now @! Developability decreases when used as a solvent.

Examples of the thermal reaction catalyst (component D) capable of thermally reacting an epoxy group used in the present invention include aliphatic amines such as ethylamine, butylamine, amylamine, and n-hexylamine, and fatty acids such as cyclohexylamine and aminodecalin. Cyclic amine, pyridine, lutidine, collidine, aniline, toluidine, N,N-dimethyl-α-naphthylamine, diphenylamine, aminoanthracene,
Aromatic amines such as triphenylamine, furfurylamine, aminopyridine, aminopicoline, aminoquinoline, aminoisoquinoline, aminodibenzofuran, aminodibenzothiophene, heterocyclic amines such as aminoacridine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetra Aliphatic polyamines such as ethylene pentaamine, diethylaminopropylamine, metaxylylene diamine, polyethylene amine, aromatic polyamines such as metaphenylene diamine, triaminobenzene, diaminotoluene, diaminodiphenylmethane, diaminodiphenylsulfone, 1゜3-diaminocyclohexane , N,N-diethyl-1,4-cyclohexanediamine, isophoronediamine, N-aminoethylpiperazine, alicyclic diamines such as piperazine, unsaturated aliphatic amines such as allylamine, diallylamine, allyldiethylamine, diaminostilbene, and the above amines. complexes with boron halides such as boron trifluoride, boron trichloride, and boron tribromide, amines containing cyanogen groups such as dicyandiamide, polyamide resins, imidazoles such as benzimidazole, benzyltetramethylenesulfonium ion, benzyl Benzylsulfonium ions such as diethylsulfonium ion, acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride, chlorenic anhydride, Further, the epoxy curing agent Ebicure manufactured by Yuka Shell Epoxy Co., Ltd. can be mentioned.

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

The blending amount of component (D) is 0.01 to 10% by weight, preferably 0.05 to 5% by weight. If this blending amount is less than 0.01% by weight, components (A) and (B) cannot be sufficiently thermally reacted during post-baking, which will be described later.
It was not possible to obtain a cured film with high solder heat resistance;
If it exceeds % by weight, the hygroscopicity of the cured film will increase,
The insulation resistance of the cured film decreases.

Examples of the photopolymerization initiator (component (E)) used in the present invention include α-diketones such as benzyl and diacetyl, acyloins such as benzoin, benzoin dimethyl ether, benzoin diethyl ether, benzoin diisopropyl ether, and benzoin. Acilloin ethers such as dimethyl ketal, thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-1-sulfonic acid, thioxanthone-4-sulfonic acid, hensifhenone, 4.4"-dimethylaminobenzophenone (Michler's ketone), etc. hensifenones,
Acetophenone, p-dimethylaminoacetophenone,
α,α1-dimethoxyacetoxyacetophenone, 2,
Examples include acetophenones such as 2-dimethoxy-2-phenylacetophenone and p-methoxyacetophenone, and quinones such as anthraquinone and 1,4-naphthoquinone.

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

The blending amount of component (E) is 0.001 to 15% by weight, preferably 0.5 to 10% by weight. This amount is 0.00
If the amount is 0% by weight, sufficient photocurability cannot be imparted to the photosensitive resin composition, while if it exceeds 15% by weight, all the photopolymerization initiator is not allowed to react during photocuring. Since it cannot be involved, the storage stability of the photocured coating film may be deteriorated, and the photopolymerization initiator may precipitate from the photosensitive resin composition before curing.

In addition to the above-mentioned components (A) to (E) as essential components, the photosensitive resin composition of the present invention contains at least one ethylenically unsaturated double bond as an optional component in order to increase the sensitivity to actinic rays. A photopolymerizable compound (component (F)) having
can be used in combination.

As component (F), 1 (i [[i or an ester of acrylic acid or methacrylic acid of a polyhydric alcohol can be used.

Examples of the monohydric alcohol include methanol, ethanol, propatool, isopropyl alcohol, n-butanol, isobutanol, m-butanol, cyclohexyl alcohol, benzyl alcohol, octyl alcohol, 2-ethylhexanol, lauryl alcohol, and n-butanol.
-decanol, undecanol, cetyl alcohol, stearyl alcohol, methoxyethyl alcohol, ethoxyethyl alcohol, butoxyethyl alcohol, polyethylene glycol monomethyl alcohol, polyethylene glycol monoethyl alcohol, 2-hydroxyethyl alcohol, 2-hydroxypropyl alcohol, 2-hydroxy- 3-chloropropane, dimethylaminoethanol, diethylaminoethanol, glycidol, 2-trimethoxysilylethanol, ethylene chlorohydrin, ethylene bromohydrin, 2,3-dibromopropanol, allyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol, Examples include naphthol.

Examples of the polyhydric alcohol include ethylene glycol, 1.3-propanediol, 1.4-butanediol, 1,5-bentanediol, hexanediol, heptanediol, octanediol, nonanediol,
Dodecanediol, neopentyl glycol, 1,1.
O-decanediol, 2-butene-1,4-diol,
2-n-butyl-2-ethylpropanediol, 2-butene-1,4-diol, cyclohebutanediol, 1
．． 4-cyclohexane dimetatool, 3-cyclohexene-1,1-jetanol, polyethylene glycol (
diethylene glycol, triethylene glycol, etc.)
Polypropylene glycol (dipropylene glycol,
tripropylene glycol, etc.), polystyrene oxide glycol, polytetrahydrofuran glycol, xylylene diol, bis(β-hydroxyethoxy)benzene, 3-chloro-1,2-propanediol, 2.2
-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol, decalindiol, 1.
5-dihydroxydi1.2,3.4-tetrahydronaphthalene, 2゜5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-(hydroxymethyl)-1 , 3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, 2-methyl-1,4-butanediol, 2-methyl- 2,4-bentanediol, 1-phenyl-1,2-ethanediol, 2,2,4.4-tetramethyl-1,3-cyclobutanediol, 2,3,5.
6-tetramethyl-p-xylene-α,α1-diol, 1. 1. 4. 4-tetraphenyl-2-butyne-1,4-diol, 1,1'-bi-2-naphthol,
Dihydroxynaphthalene, 1.1°-methylene-di2
- Naphthol, biphenol, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, resorcinol, 2-methylresorcinol, 4-chlor Resorcinol, hydroquinone, phloroglucinol, pyrogallol, χ-(1-
aminoethyl)-p-hydroxybenzyl alcohol,
2-amino-2-ethyl-1,3-propanediol,
2-amino-2-methyl-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, N-n-butylgetanolamine, N-ethylgetanol Amine, 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-bis(hydroxymethyl)-
Examples include 2,2° 2 IT=nitrilotriethanol. Among these esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohols, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,
Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, neopentyl glycol diacrylate, Particularly preferred are neopentyl glycol dimethacrylate, sorbitol hexaacrylate, sorbitol hexamethacrylate, sorbitol pentaacrylate, sorbitol pentamethacrylate, and the like.

Furthermore, as component (F), it is also possible to use acrylamide or methacrylamide of monoamines or polyamines.

Examples of the monoamines include monoalkylamines such as ethylamine, butylamine, amylamine, hexylamine, octylamine, cyclohexylamine, and 9-aminodecalin, allylamine, metaallylamine,
Monoalkenylamines such as benzylamine, aniline,
Examples include aromatic amines such as toluidine and p-aminostyrene.

Examples of the polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, hexamethylenebis(2-aminopropyl)amine, diethylenetriamine, triethylenetetraamine, polyethylenepolyamine, and 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, diaminostilbene, methylene dianiline, 2,4-bis(4
-aminobenzyl)aniline, aminophenyl ether, and the like.

Furthermore, as component (F), an allyl compound such as formic acid,
Mono- or dicarboxylic acids such as acetic acid propionic acid, butyric acid, lauric acid, benzoic acid, chlorobenzoic acid, malonic acid, oxalic acid, glitaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, chlorendic acid, etc. mono- or diallyl esters of disulfonic acids such as triallyl trimellitate, benzenedisulfonic acid, naphthalenedisulfonic acid, diallylamine, N,N''-diallyl oxalate diamide,
1,3-diallylurea, diallyl ether, etc. are also used.

Further, as component (F), for example, divinylbenzene, p-
Allyl styrene, p-isopropenyl styrene, divinyl sulfone, ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl phthalate,
Polyvinyl compounds such as divinyl phthalate and divinyl terephthalate, ester compounds of acrylic acid or methacrylic acid having ionic groups such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, and methacryloyloxyphenyltrimethylammonium chloride are also used.

Furthermore, as component (F), commercially available photopolymerizable monomers or oligomers, such as Alonix M57QQ, M6100, M8O30, M152, M manufactured by Toagosei Kagaku Kogyo Co., Ltd.
Acrylate sevenmers such as 2O3, M215, M315, M325, etc. 1 NK ester 2G manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
4G, 9G, 14G, ABPE-4, A-TMPT,,
U-4HA.

CB-1, CBX-1, Nipponka Leaf Juice! l! KAYARA
DR604, DPCA-30, DPCA-66, K
Acrylate or methacrylate sevenmers such as AYAMER PM-1, PM-2, Photomer 4061.5007 manufactured by San Nopco Co., Ltd. 1 Lipoxy VR6 manufactured by Showa Kobunshi Co., Ltd.
Also used are epoxy acrylates such as 0, VR90, and 5p1509, and spiran resins having a spiro 7 secur structure and an acrylic or methacrylic group such as Subirasoku E-4000X and 03000 manufactured by the same company.

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

The blending amount of component (F) is 60% by weight or less, preferably 3% by weight or less, from the viewpoint of thermal shock resistance and solvent resistance of the coating film after photocuring.
It is 0% by weight or less.

A high molecular weight polymer may be added to the photosensitive resin composition of the present invention in order to further enhance the film properties of the composition. High molecular weight polymers include acrylic acid, methacrylic acid, acrylic esters, homopolymers and copolymers of methacrylic esters, such as polyacrylic acid,
Polymethyl methacrylate, a copolymer of acrylic acid and methyl methacrylate, polyvinyl chloride, polyvinyl acetate 1, nylon, and the like can be used.

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

The blending amount of the high molecular weight polymer is from the component (A) to
Preferably 0.1 to 100 parts by weight of (E)
It is 30 parts by weight, particularly preferably 5 to 25 parts by weight.

The photosensitive resin composition of the present invention preferably contains a heat addition polymerization inhibitor to prevent polymerization before heat curing. Examples of thermal addition polymerization inhibitors include hydroquinone, p-methoxyphenol, p-butylcatechol, 2,6
-Zim-butyl-p-cresol, β-naphthol,
Aromatic hydroxy compounds such as pyrogallol, quinones such as benzoquinone and p-toluquinone, naphthylamine, amines such as lysine, p-toluidine, and phenothiazine, aluminum salts or ammonia salts of N-nitrosophenylhydroxylamine, floranil, and nitrobenzene. can be mentioned. These compounds may be used alone or in combination of two or more.

The blending amount of the heat addition polymerization inhibitor is preferably O0001 to 15 parts by weight per 100 parts by weight of the total amount of components (A) to (E).
Parts by weight, particularly preferably 0.005 to 5 parts by weight.

Furthermore, the photosensitive resin composition of the present invention includes a tackifier, an adhesion aid, a dispersant, a plasticizer, an anti-sagging agent, a leveling agent,
Auxiliary additives such as antifoaming agents, flame retardants, brighteners, colorants, etc. may be added as necessary.

Addition of a tackifier or adhesion aid increases the adhesion of the photosensitive resin composition to the substrate after photocuring, and this effect is particularly pronounced when laminated to copper-mounted laminates and solder-mounted laminates. Ru.

A dispersant is used to improve the dispersibility, storage stability, etc. of a photosensitive resin composition. The necessity of blending plasticizers, anti-sagging agents, leveling agents, and antifoaming agents depends on the method of using the photosensitive resin composition, that is, the method of creating a coating film of the photosensitive resin composition, and the type and composition used. 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 anti-foaming properties), but also multiple additive effects. For example, dispersants may also act as plasticizers, leveling agents, and antifoaming agents for photosensitive resin compositions; It also has an effect on the glossiness of photosensitive resin compositions, and may act as a brightening agent.

Examples of tackifiers or adhesion aids include novolak resin, polyvinylethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, and acrylic. Examples include aromatic, aliphatic, or alicyclic petroleum resins. These compounds alone or 2f! A mixture of the above is used.

The amount of the tackifier or adhesion aid is the above component (A) ~
Preferably 0.05 parts by weight per 100 parts by weight of the total amount of (E)
-40 parts by weight, particularly preferably 0.05-30 M parts.

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.

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

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

Examples of leveling agents include ANTIGEL and BLISTERFREE manufactured by Schuenigemann (West Germany).
84 etc. are used.

As the antifoaming agent, silicone oil or the like is used, for example.

Furthermore, for example, dispersant BM1000, BMIloo, anti-settling agent and thickening anti-sag agent BM-TX, anti-foaming agent BM1200, fluidity improver BM100O1, adhesion improver BM340, etc. manufactured by BM Hemie (West Germany) may be used. can.

These dispersants, plasticizers, anti-sagging agents, leveling agents,
The blending amounts of the antifoaming agent and brightening agent are as follows: Components (A) to (E)
), preferably 40 parts by weight in total.
The total amount is not more than 20 parts by weight, particularly preferably not more than 20 parts by weight.

Examples of flame retardants include inorganic flame retardants such as antimony dioxide, zirconium hydroxide, barium metaborate, magnesium hydroxide, and aluminum hydroxide, tetrabromobisphenol A, chlorinated paraffin, perchloropentacyclodecane, Halogen-based flame retardants such as tetrabromobenzene and chlorinated diphenyl, and chlorinated phosphonitrile derivatives, vinyl phosphonates, allyl phosphonates, tris (β-chloroethyl) phosphonates,
Phosphorous flame retardants such as tricresyl phosphonate and ammonium phosphate are used.

The amount of the combustion agent No. 11 to be blended is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the total amount of components (A) to (E).

As a brightening agent, for example, Schunigemann AG (West Germany)
ANTIGEL manufactured by Manufacturer Co., Ltd. is used.

Examples of colorants include inorganic pigments such as titanium oxide, carbon blank, and iron oxide, organic dyes such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes, and phthalocyanines such as phthalocyanine blue and phthalocyanine green. 1 Green C is used for pigment-based or ab-based organic pigments, and Dia Resin Red Z1 Blue manufactured by Mitsubishi Chemical Industries, Ltd.

The amount of the colorant to be blended is preferably 5 parts by weight or less, particularly preferably 2 parts by weight or less, based on 100 parts by weight of the total amount of components A to E.

The photosensitive resin composition of the present invention is obtained by dissolving each of the above components in an organic solvent.

Examples of organic solvents used at this time include acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, ethers such as dioxane, tetrahydrofuran, ethylene glycol diethyl ether, diethylene glycol diethyl ether, halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, acetic acid Ethyl, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-
Esters such as butoxyethyl acetate, alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, butyl alcohol, and N,N-dimethylformamide, N,N-dimethylacetamide, N- Examples include polar solvents such as methylpyrrolidone, dimethylsulfoxide, and hexamethylphosphoramide. These organic solvents may be used alone or in combination of two or more.

When forming an image using the photosensitive resin composition of the present invention obtained in this manner, the photosensitive resin composition is applied to a substrate, dried to scatter the solvent, and then a mask is applied to the dried coating film. The films are exposed in layers and developed with an organic solvent.

Examples of methods for applying the photosensitive resin composition of the present invention onto a substrate include a spray method, a dip coating method, a brush coating method, a roller coating method, a flow coater method, a curtain coater method, and a screen printing method. In particular, in the case of coating a 4-layer film or a printed circuit board, a spray method, a roller coating method, a flow coater method, a curtain coater method, a screen printing method, etc. are preferable.

The drying temperature of the coating film for scattering the solvent is selected depending on the solvent used, but is usually 20 to 180°C, preferably 20 to 130°C.

The exposure device used for photocuring the photosensitive resin composition of the present invention is not particularly limited, but it is preferable to use an ultraviolet exposure device equipped with a high-pressure mercury lamp that emits ultraviolet light in the vicinity of 300 to 400 nm.

Examples of the organic solvent used as a developer for the photosensitive resin composition of the present invention include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, dioxane, tetrahydrofuran, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. Ethers such as methylene chloride, 1.2-dichloroethane, 1.1 halogenated hydrocarbons such as 1-trichloroethane, ethyl acetate, 2
- Esters such as methoxyethyl acetate, 2-ethoxyethyl acetate, and 2-butoxyethyl acetate, alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and L-butyl alcohol, and N,N -dimethylformamide, N, N-
Examples include polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and hexamethylphosphoramide. These compounds may be used alone or in combination of two or more. Particularly non-flammable solvents 1, 1
．． It is preferable to use 1-trichloroethane (chlorocene) or a mixed solvent of non-flammable 1.1.1-trichloroethane and other solvents.

Further, surfactants such as polyoxyethylene glycol octylphenyl monoether and stearic acid sulfate ester can also be added to the developer.

Further, the photosensitive resin composition of the present invention is usually post-baked after photocuring. Thereby, a cured film with improved adhesion, soldering heat resistance, and hardness can be obtained.

Post-bake temperature is 50-200℃, preferably 80℃
~150°C.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Production Example 1 (Synthesis of modified resin: component (B)) Epoxidized resin (EOCN-102 manufactured by Nippon Kayaku Co., Ltd.) 165 g (1
mol) and 0.5 g of 2,6-lutidine were dissolved in 130 g of methyl ethyl ketone.

Next, 27.5 g of methacrylic acid (0.32 mol, 40 mol % based on 1 equivalent of epoxy group of the epoxidized resin)
was dissolved in 100 g of methyl ethyl ketone, added dropwise to the methyl ethyl ketone solution of the epoxidized resin at room temperature, and then reacted at 80° C. for 6 hours. The reaction solution was poured into 31 volumes of ice water/methanol (volume ratio 1/1) to precipitate the modified resin, which was a reaction product, and was dried under reduced pressure. The NMR spectrum of the product showed that 40% of the epoxy groups of the epoxidized resin had reacted with methacrylic acid.

Production Example 2 (Synthesis of Modified Resin: Component (B)) 165 g (1 mole) of an epoxidized resin (EOCN102S manufactured by Nippon Kayaku Co., Ltd.) and 0.5 g of 2,6-lutidine were dissolved in 200 g of methyl ethyl ketone.

Next, 84.6 g of phthalic acid mono (β-acryloyloxyethyl) ester (0.32 mol, 60 mol % based on 1 equivalent of epoxy group in the epoxidized resin) was dissolved in 175 g of methyl ethyl ketone, and the epoxidized resin was dissolved at room temperature. The mixture was added dropwise to a methyl ethyl ketone solution and reacted at 80°C for 6 hours.

The reaction solution was diluted with 312 ice water/methanol (volume ratio 1/1).
The reaction product, the modified epoxidized resin, was precipitated and dried under reduced pressure. The NMR spectrum of the product showed that 40% of the epoxy groups of the epoxidized resin had reacted with phthalic acid mono (β-acryloyloxyethyl) ester.

Example 1 87.5 g of a 60% by weight methyl ethyl ketone solution of the modified resin obtained in Production Example 2, 15 g of epoxidized resin (EOCN-102 manufactured by Nippon Kayaku Co., Ltd.), 15 g of epoxidized resin (BREN manufactured by Nippon Kayaku Co., Ltd.) , polymethyl methacrylate 5
g, Alonisox M315 manufactured by Toagosei Chemical Industry Co., Ltd.
og, trimethylolpropane triacrylate Log
,) 10 g of liglycidyl isocyanurate, 3 g of penzoin dimethyl kecur, 0.03 g of aluminum salt of N-nitrosophenylhydroxylamine, 1479 g of epoxy curing agent Ebicure manufactured by Shell Epoxy Co., Ltd.
0.25 g of benzimidazole, 25 g of Diaresin Green C0 manufactured by Mitsubishi Kasei, methyl ethyl ketone 7.
5 g and 40 g of 2-ethoxyethyl acetate, 3
The mixture was weighed into an eggplant flask and uniformly melted at 40°C to prepare an uninvented photosensitive resin composition.

(Evaluation of photosensitive resin composition +i
After applying the photosensitive resin composition obtained in Example 1, the temperature was 80°C.
It was dried for 30 minutes to produce a photosensitive resin layer with a thickness of 70 μm. Overlap the mask films and set the exposure amount I J
A clear image was obtained by developing for 3 minutes using 7i, 1.1.1-)lichloroethane (chlorocene) irradiated with UV light of /cd. After post-baking at 130°C for 1 hour,
When cross-cutting was performed with a knife and a peeling test was performed using a commercially available tape, no peeling was observed, indicating that the photosensitive resin composition of the present invention has excellent adhesion to the copper plate. Furthermore, when immersed in a 260°C solder bath for 20 seconds, no peeling or blistering was observed, indicating excellent soldering heat resistance.

When a copper through-hole printed circuit board was used instead of the copper-clad glass epoxy laminate and evaluated in the same manner as described above, the same results as the copper-clad glass epoxy laminate were obtained, indicating that the photosensitive resin composition of the present invention It has been shown that this is suitable as a resist for printed circuit boards, especially as a resist for solder.

Examples 2 to 17 Photosensitive resin compositions of the present invention were prepared in the same manner as in Example 1 using the compounds shown in Table 1 in the proportions shown in the table.

These photosensitive resin compositions were evaluated in the same manner as in Example 1 using copper through-hole printed circuit boards, and were found to have excellent adhesion and soldering heat resistance, and were suitable as resists for printed circuit boards for soldering. Indicated.

Margin Comparative Examples 1 to 4 Photosensitive resin compositions were prepared in the same manner as in Example 1 using the compounds shown in Table 2 in the proportions shown in the table.

When these photosensitive resin compositions were evaluated in the same manner as in Example 1, peeling was observed after tape removal 'f4i, and peeling was observed when immersed in a solder bath at 260°C for 20 seconds. The adhesion and soldering heat resistance were lower than that of the photosensitive resin composition.

Table 2 (Exhibit 1) Epoxidized resin manufactured by Nippon Kayaku Co., Ltd., EOCN-1
022) Epoxy curing agent manufactured by Yuka Shell Epoxy Co., Ltd. 3) Dye manufactured by Mitsubishi Kasei Co., Ltd. (Effects of the invention) The photosensitive resin composition of the present invention can be used to cure metals such as copper, solder surfaces, etc., such as epoxy resins, glass epoxy resins, It has excellent adhesion with resins such as phenolic resin and paper, and has excellent soldering heat resistance.It also has high sensitivity and resolution to actinic rays, and the electrical insulation properties of the cured film.
It has excellent mechanical properties and can be developed with nonflammable solvents such as chlorocene.

The photosensitive resin composition of the present invention is suitable as a photoresist for printed circuit boards such as copper through-hole printed circuit boards made of copper-clad glass epoxy laminates, solder through-hole printed circuit boards, etc., and particularly as a solder resist for printed circuit boards. be.

Furthermore, the photosensitive resin composition of the present invention can be used in plating resists, etching resists, various printing resin plates, photoadhesives, etc., and can also be used in fields where it is preferable to use photosensitive materials, especially electronic components. It can also be used in a wide range of applications such as permanent insulation films and interlayer insulation films.

Claims (1)

[Scope of Claims] (A) 5 to 60 weight epoxidized resin obtained by epoxidizing a novolak resin obtained by reacting a phenol having at least one selected from a halogen atom and an alkyl group with an aldehyde compound %, (B) 20 to 75% by weight of a modified resin obtained by reacting the epoxidized resin of (A) with an unsaturated carboxylic acid, (C) at least one epoxy compound (however, the above components A and B (excluding) 0.01 to 45% by weight, (D) 0.0 of a thermal reaction catalyst capable of thermally reacting an epoxy group
1 to 10% by weight, and (E) 0.001 to 15% by weight of a photopolymerizable initiator capable of photopolymerizing an unsaturated group.