JPH0820736B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photopolymerizable composition that can be polymerized and cured by irradiation with actinic rays. More specifically, the present invention relates to a photopolymerizable composition having good adhesion to a metal surface, particularly copper, and having no red discoloration or peeling off. More specifically, the present invention relates to a photopolymerizable composition which is easily photocurable and is useful for forming a photoresist which is resistant to various liquids for plating and etchants.

[Conventional technology]

Japanese Patent Publication Sho-45- used in the manufacture of printed wiring boards
The dry film photoresist as seen in Japanese Patent No. 25231 is laminated on a copper clad laminate (substrate), is irradiated with an actinic ray through a document having a wiring pattern, and then an unexposed portion is exposed using an appropriate developing solution. A melted and cured image is obtained on the substrate. Using the obtained cured image as a resist, the exposed copper is modified by various methods such as etching, plating or anodizing to manufacture a printed circuit board. However, the dry film resist has a weaker adhesiveness to the metal surface as compared with the liquid photoresist, and various undesirable phenomena occur during etching or plating. For example, when the etching liquid is sprayed or dipped in the plating liquid, the liquid penetrates between the resist and the copper substrate, the resist is separated, and floats up from the copper substrate, under-etching, under-plating (plating). Such phenomenon occurs. As a result, the edge of the image becomes unclear, the resist image is lost, and a pattern with the desired accuracy cannot be obtained, and a large number of substrates are wasted.

In manufacturing a printed wiring board using a dry film resist, when a resist pattern is created on a substrate, the resist pattern part may be adhered to the entire surface of the substrate. It is called a hole), and a printed wiring board is created on both the front and back surfaces of the board, and the through wiring is used. When making a printed wiring in which wiring on both the front and back sides is electrically conducted through the inside of the hole, it is necessary to stretch the resist film above or below the through hole without adhering the entire resist film to the metal surface. There is (called the tenting method). This is to prevent the metal layer inside the through hole from being etched when the printed wiring is created by etching. In the case of such a tenting method, the resist film formed is in close contact with the substrate only in a very small area around the exit of the through hole, and the other parts of the film are owing to their own cohesive force. It is required to have an adhesive property that is held on the surface and does not peel off even with the spray of the commonly used spray type etching method, but since it is not necessarily large enough, the etching solution may seep into the side of the tent film. .

In order to improve these problems, a method of preliminarily surface-treating a metal surface has been proposed (Japanese Patent Publication No. 54-5292).
No. 51-64919, JP-A-51-64920).

On the other hand, a method of improving the adhesiveness by adding various compounds in the photosensitive resin layer has been proposed (Japanese Patent Publication No. 50-9177, Japanese Patent Publication No. 54-5,292, Japanese Patent Publication No. 55-22,481).
JP-A-51-64,919, JP-A-51-64,920, JP-A-51-64,920
50-63,087, JP-A-51-2724, JP-A-53-702,
JP-A-53-124,541, JP-A-53-124,594, JP-A-54
-133,585, JP-A-54-133,586, JP-A-55-65,947
Japanese Patent Publication No. 57-46,053, Japanese Patent Publication No. 57-46,054,
56-11,904, JP-B-57-21,697, JP-A-56-75,642
JP-A-56-67,844, JP-B-57-40,500, JP-A-SHO
56-99,202, JP-A-56-100,803, JP-A-57-60,32
7, JP-A-57-62,047, DAS2448850, US4629679
JP-B-57-49,894, JP-A-57-148,392, JP-A-57-192,946, JP-A-58-100,844, JP-A-59-11.
3,432, JP-A-59-125,725, JP-A-59-125,726
JP-A-59-125,727, JP-A-59-125,728, JP-A-59-152,439, JP-A-59-154,440, JP-A-59-15.
4,441, JP-A-59-165,051, JP-A-60-12,543,
JP-A-60-12,544, JP-A-60-135,931, JP-A-60
-138,540, JP60-146,233, JP61-4,038
No. 61, JP-A-61-6644, JP-A-61-6,646, JP-A-61
-166,541, JP-A-61-172,139, JP-A-61-186,95
2, JP-A 61-190,330, JP-A 61-198,146, JP-A 61-223,836, JP-A 61-282,835, JP-A 61-
360,237, JP-A-62-91,935, JP-A-62-96,939
JP-A-62-180,354, JP-A-62-180,355, JP-A-62-180,356, JP-A-62-180,357, JP-A-62-18
1,303, JP 62-208,042, JP 62-240,950
JP-A-62-277,405, JP-A-62-286,035, JP-A-62-290,702, JP-B-63-13526, JP-A-63-24,
243, JP-A-63-57,622, JP-A-63-61,241).

"Problems to be solved by the invention" It is clear that the former method is superior to the former method in that new additional steps are required, but the copper exposed surface of the substrate after development is The phenomenon of reddishness is observed, which adversely affects post-processing such as etching, plating, and soldering, decolorizes dyes, inhibits photopolymerization reaction,
Alternatively, it has various problems such as poor solubility in the photopolymerizable resin composition and many inconveniences in production. Particularly, as an additive effective for improving the adhesiveness, Japanese Patent Laid-Open No.
The compound described in No. 60-12544 (the compound of the present application (I)) is known, but it has not been sufficient in that it causes red discoloration and peeling.

[Object of the Invention]

An object of the present invention is to provide a photopolymerizable composition which does not have the above-mentioned problems, has good adhesiveness to a metal surface, and is free from red discoloration and peeling.

More particularly, it is to provide photopolymerizable compositions useful in forming dry film resists utilized in the manufacture of printed circuit boards.

[Means for solving problems]

The present inventors have developed a photopolymerizable composition containing a heterocyclic compound represented by the general formulas (I) and (II) shown below, and have good adhesiveness to a metal surface without causing red discoloration or peeling off. Have been found to improve.

That is, the object of the present invention is at least (1) to (4).
It was achieved by a photopolymerizable composition characterized by containing

(1) a non-gaseous ethylenically unsaturated compound having at least two terminal unsaturated groups and capable of forming a polymer, (2) a thermoplastic organic polymer binder, (3) active by actinic rays Photopolymerization Initiator System (4) Heterocyclic Compounds Represented by General Formulas (I) and (II) General Formula (I) R ₁ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an amino group, or a substituted amino group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted alkyl group,
Represents an aryl group or an aralkyl group, R ₄ and R ₅ are a hydrogen atom, an alkyl group, a substituted alkyl group,
It represents an aryl group or an aralkyl group and may form a pyrrolidine, piperidine, morpholine or N-substituted piperazine nucleus together with an N atom. X is an oxygen atom or a sulfur atom Or N—R ₆ [R ₆ represents a hydrogen atom, an alkyl group or an aryl group. ] And Y represents an oxygen atom or a sulfur atom.

General formula (II) Further, in R _{1 to} R ₁₁ , the alkyl group has 1 to 20 carbon atoms.
Are preferred.

The preferred addition amount of these heterocyclic compounds is 0.001 to 0.1% by weight of the compound of formula (I) relative to the solid content of the photopolymerizable composition, and 0.01 to 0.5% by weight of the compound of formula (II). Is the compound of formula (I): 0.01 to 0.04% by weight, the compound of formula (II): 0.04 to 0.2% by weight.

When the amount of the compound of the formula (I) added is 0.001% by weight or less, the adhesiveness of the resist is insufficient, so that the resist may be scooped up or lifted during etching, or fine lines may be peeled off during development.

If the amount of the compound added is 0.1% by weight or more, the copper plate tends to turn red and peel off easily.

When the amount of the compound of the formula (II) added is 0.01% by weight or less, the effect of preventing red discoloration is lost.

When the amount of the compound added is 0.5% by weight or more, the leuco dye develops color in the storage state and peeling off occurs.

The preferred ethylenically unsaturated compound used in the present invention is a compound having at least two terminal unsaturated groups and capable of photopolymerization upon irradiation with actinic rays. Hereafter abbreviated as polyfunctional monomer.

Specifically, Japanese Patent Publication No. 35-5,093, Japanese Patent Publication No. 35-14,
The following compounds are described in Japanese Patent Publication No. 719, Japanese Patent Publication No. 44-28,727 and the like.

First, as acrylic acid esters and methacrylic acid esters, there are polyacrylates and polymethacrylates of polyhydric alcohols (herein, “poly” means diacrylate or higher). As the polyhydric alcohol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polycyclohexene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran, cyclohexanediol, xylylenediol, di- (β-hydroxyethoxy) benzene, glycerin, di Glycerin, neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol,
Sorbitan, sorbitol, butanediol, butanetriol, 2-butene-1,4-diol, 2-n-butyl-2-ethyl-propanediol, 2-butyne-1,4
-Diol, 3-chloro-1,2-propanediol, 1,4
-Cyclohexanedimethanol, 3-cyclohexene-
1,1-dimethanol, decalin diol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-
Propanediol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,5-dimethyl-2,5-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2
-Diphenyl-1,3-propanediol, dodecanediol, mezoerythritol, 2-ethyl-1,3-hexanediol, 2-ethyl-2- (hydroxymethyl)-
1,3-propanediol, 2-ethyl-2-methyl-1,3
-Propanediol, heptanediol, hexanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol, hydroxyethylresorcinol, 2
-Methyl-1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol,
Pentanediol, 1-phenyl-1,2-ethanediol, propanediol, 2,2,4,4-tetramethyl-1,3-
Cyclobutanediol, 2,3,5,6-tetramethyl-p-
Xylene-α, α'-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,2, 6-trihydroxyhexane, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylenedi-2-naphthol, 1,
2,4-benzenetriol, biphenol, 2,2'-bis (4-hydroxyphenyl) butane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, 3,4-dihydroxyhydrocinnamic acid, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methyl-2,4,6-tri Hydroxybenzoate, phloroglucinol, pyrogallol, resorcinol, glucose, α- (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, 2,2-bis (hydroxymethyl) -2,2 ', 2 "-nitrilotriethanol, 2,2-bis (hydroxymethyl) propio Nick Acid, 1,3-
Bis (hydroxymethyl) urea, 1,2-bis (4-pyridyl) -1,2-ethanediol, Nn-butyldiethanolamine, diethanolamine, N-ethylenediethanolamine, 3-mercapto-1,2-propanediol, 3-piperidino-1,2-propanediol, 2
There are-(2-pyridyl) -1,3-propanediol, triethanolamine, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenyl sulfone and the like. Among these acrylic acid esters and methacrylic acid esters, the most preferable ones are ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol because of their easy availability. Dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetrapropylene glycol diacrylate, dodecane propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
Pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylate, 1,3-propanediol diacrylate, 1,2,4- Examples thereof include butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, and ethylene oxide-added trimethylolpropane triacrylate.

On the other hand, examples of acrylamides and methacrylamides include methylenebisacrylamide, methylenebismethallylamide, ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylene, bis (2-aminopropyl) amine, and diethylenetriaminediamine. , Heptamethylenediamine,
Octamethylenediamine and polyamines interrupted by heteroatoms, polyamines having a ring (for example, phenylenediamine, xylylenediamine, β- (4-aminophenyl) ethylamine, diaminobenzitzacitide, diaminotoluene, diaminoanthraquinone, diaminofluorene, etc. ) Polyacrylamide and polymethacrylamide.

Examples of the allyl compound include diallyl esters of dicarboxylic acids such as phthalic acid, terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid, and oxalic acid, for example, anthraquinone disulfonic acid, benzenedisulfonic acid, 2,5-dihydroxy-p. -Benzenedisulfonic acid,
Examples include diallyl esters of disulfonic acid such as dihydroxynaphthalenedisulfonic acid and naphthalenedisulfonic acid, and diallylamide.

Examples of vinyl ether compounds include polyvinyl ethers of the above polyhydric alcohols, such as ethylene glycol divinyl ether, 1,3,5-tri-β-vinyloxyethoxybenzene, 1,3-di-β-vinyloxyethoxybenzene, and glycerol. Examples include trivinyl ether.

As vinyl esters, divinyl succinate,
There are divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate, divinyl butane-1,4-disulfonate and the like.

Examples of the styrene compound include divinylbenzene, p-allyl styrene and p-isopropene styrene.

Compounds having two or more different addition-polymerizable unsaturated bonds such as N-β-hydroxyethyl-β- (methacrylamido) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide and allyl methacrylate. Are also preferably used in the present invention.

Furthermore, the reaction product obtained by reacting a polyol compound having at least two hydroxyl groups with a polyisocyanate compound having a slight excess of at least two isocyanate groups has at least one hydroxyl group and at least one ethylenically unsaturated group. A polyfunctional urethane compound having at least two ethylenically unsaturated groups obtained by reacting a compound is also suitably used in the present invention.

These polyfunctional monomers can be used alone or in combination of two or more kinds, and the solid content of the photopolymerizable composition is 5% or less.
It is used in the range of 90 to 90% by weight, preferably 15 to 60% by weight.

The binder used in the photopolymerizable composition of the present invention is selected from a wide variety of synthetic, semi-synthetic and natural polymer substances that satisfy the following conditions. That is, the compatibility with the polyfunctional monomer, the photopolymerization initiator and the heterocyclic compound of the present invention is good enough not to cause demixing during the manufacturing process from preparation of the coating liquid to coating and drying. Depending on the usage of, for example, when used in a photoresist for tenting, the polymer strength, stretchability, abrasion resistance,
The chemical resistance is appropriate, and the molecular weight, intermolecular force, hardness, softening temperature, crystallinity, fracture elongation, etc. of the polymer are appropriate.

Specific examples of the binder include chlorinated polyethylene such as chlorinated polyethylene and chlorinated polypropylene, and poly (meth) acrylic acid alkyl ester such as polymethylmethacrylate (wherein the alkyl group is a methyl group, an ethyl group, a butyl group, etc.) ), (Meth) acrylic acid and (meth)
Acrylic acid alkyl ester (alkyl group same as above), poly (meth) acrylic acid, (meth) acrylic acid alkyl ester (alkyl group same as above) and acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene etc. Copolymer with at least one kind of monomer, polyvinyl chloride, copolymer of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymer of vinylidene chloride and acrylonitrile, copolymer of vinyl acetate and vinyl chloride, Polyacrylonitrile, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile and butadiene and styrene, copolymer of styrene and unsaturated dibasic acid anhydride such as maleic anhydride, polyvinyl butyral, styrene butadiene rubber, Chlorinated rubber, cyclized rubber, acetyl cellulose Scan the like homopolymers or copolymers of such.

In the case of a copolymer, the content ratio of its component monomers can take a wide range of values, but it is generally preferable that the content of the other copolymerization monomer is 5% or more. Further, even polymers other than these can be used as the binder of the present invention as long as they satisfy the above conditions.

Among the above-mentioned polymers, those which are particularly preferably used as the binder of the present invention include chlorinated polyethylene, chlorinated polypropylene, polymethylmethacrylate, methylmethacrylate-acrylonitrile copolymer (the molar content of methylmethacrylate is 20 to 80%). ), Vinyl chloride-acrylonitrile copolymer (vinyl chloride molar content 20 to 80%),
Vinylidene chloride-acrylonitrile copolymer (vinylidene chloride molar content 20-80%), styrene-maleic anhydride copolymer, Japanese Patent Application No. 59-114736 (binder is methyl methacrylate / methacrylic acid / 2-ethylhexyl) Methacrylate / benzyl methacrylate quaternary copolymer), JP-B-54-34327 (the binder is, for example, a methyl methacrylate / methacrylic acid / 2-ethylhexyl / methacrylic acid terpolymer), JP-B-54 55-38961 (the binder is, for example, styrene / maleic acid mono-n-butyl ester copolymer), JP-B-54-25957 (the binder is, for example, styrene / methyl methacrylate / ethyl acrylate / methacrylic acid). Quaternary copolymer), JP-A-52-99810 (binder is, for example, benzyl methacrylate / methacrylic acid copolymer), JP-B-58- No. 12577 (Binder is, for example, acrylonitrile / methacrylic acid 2-
Ethylhexyl / methacrylic acid terpolymer)
And JP-B-55-6210 (the binder is, for example, a terpolymer of methyl methacrylate / ethyl acrylate / acrylic acid and styrene partially esterified with isopropanol /
Examples of the binder include the maleic anhydride copolymers (which are two types) and the like.

These polymers may be used alone as a binder, but polymers that are compatible with each other to the extent that demixing does not occur during the manufacturing process from preparation of two or more coating solutions to coating and drying. It can be used as a binder by mixing at an appropriate ratio.

The molecular weight of the polymer used as the binder can take a wide range of values depending on the type of polymer, but in general,
5,000 to 2,000,000, more preferably 50,000 to 1,000,00
Those in the range of 0 are preferably used in the present invention. The amount of binder is 5 to 95% by weight, preferably 40 to 80% by weight, based on the solids of the photopolymerizable composition.

On the other hand, as the photopolymerization initiator used in the present invention, conventionally known ones can be preferably used, for example, J.
There are carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by Coser. Typical examples of the carbonyl compound include benzophenone and 4,4′-bis (dimethylamino).
Benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-
Dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, fluorenone, acridone and benzoin, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal and the like.

Examples of the organic sulfur compound include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol and ethyltrichloromethanesulfenate.

Examples of 2,4,5-triarylimidazole dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl)-
4,5-Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
Examples include 4,5-diphenylimidazole dimer and 2- (p-methoxyphenyl) 4,5-diphenylimidazole dimer.

Examples of the polyhalogen compound include carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, and JP-A-53-133428 and JP-B-57.
-1819, Japanese Patent Publication No. 57-6096 and U.S. Patent No.
Mention may be made of the compounds disclosed in 3615455.

These compounds may be used alone or in combination of two or more. Preferred combinations include, for example, a combination of 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole or leucocrystal violet, and US Pat. No. 342715.
4,4'-bis (dimethylamino) benzophenone and benzophenone or benzoin methyl ether as described in U.S. Pat. No. 4,239,850 and benzoyl-N-methylnaphthothiazoline as described in U.S. Pat.
Combination of 4-bis (trichloromethyl) -6-4-methoxyphenyltriazole, combination of dimethyloxanthone and 4-dialkylaminobenzoic acid ester described in JP-A-57-23602, JP-A-57- No. 189536, and a mixed system of three kinds of 4,4′-bis (dialkylamino) benzophenone and benzophenone and a polyhalogen compound.

As the peroxide, di-t-butyl peroxide,
Examples include benzoyl peroxide and methyl ethyl ketone peroxide.

The redox compound is composed of a combination of a peroxide and a reducing agent, and includes ferrous ion and persulfate ion, ferric ion and peroxide, and the like.

Examples of the azo and diazo compounds include α, α′-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, and a diazonium salt of p-aminodiphenylamine.

Examples of the halogen compound include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, naphthalene sulfonyl chloride, phenyl tribromomethyl sulfone, and tris (trichloromethyl) -s-triazine.

Examples of the photoreducible dye include rose bengal, erythrosine, eosin, acriflavine, riboflavin, and thionine.

The content of these photopolymerization initiators and their combination systems is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyfunctional monomer.

It is preferable to add a thermal polymerization inhibitor to the photopolymerizable composition used in the present invention. Specific examples of the thermal polymerization inhibitor include, for example, p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone,
t-butylcatechol, pyrogallol, cuprous chloride, chloranil, naphthylamine, β-naphthol, 2,6-
Examples include di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, organic copper, and methyl salicylate. These thermal polymerization inhibitors are added in an amount of 0.001 to 5 with respect to the polyfunctional monomer.
It is preferably contained in the range of% by weight.

In the present invention, in order to control the physical properties of the film,
A plasticizer may be added, and typical examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
Phthalic acid esters such as diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, diaryl phthalate, dimethylglycose phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glyco Rate, butylphthalyl butyl glycolate, glycol esters such as triethylene glycol dicaprylate, phosphates such as tricresyl phosphate, triphenyl phosphate, diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl Aliphatic dibasic acid esters such as sebacate, dioctyl sebacate, dibutyl malate, Emissions Zen sulfonamide, p- toluenesulfonamide, amides such as N-n-butyl acetamide, triethyl citrate, glycerin triacetyl ester, and butyl laurate.

A combination system of an organic halogen compound and a leuco dye can be mixed in the photopolymerizable composition of the present invention.

Examples of organic halogen compounds having such a function include halogenated hydrocarbons, halogenated alcohol compounds, halogenated carbonyl compounds, halogenated ether compounds, halogenated ester compounds, halogenated amide compounds, and halogenated sulfone compounds. Can be mentioned.

Examples of halogenated hydrocarbons include carbon tetrabromide, iodoform, 1,2-dibromoethane, 1,1,2,2 tetrabromoethane, 1,1-bis (p-chlorophenyl) 2,2,2- Trichloroethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3-tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene , Hexachlorocyclopentanediene, dibromocyclohexane and the like.

Examples of halogenated alcohol compounds include 2,2,2-
Trichloroethanol, tribromoethanol, tribromoethanol, 1,3-dichloro-2-propanol,
1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-
tert-butyl alcohol, 2,2,3-trichlorobutane-
1,4-diol etc. can be mentioned.

Examples of carbonyl halide compounds are 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone,
Dibromocyclohexanone etc. can be mentioned.

Examples of the halogenated ether compound include 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether, di (2-bromoethyl) ether, 1,2-dichloroethyl ethyl ether and the like.

The halogenated ester compound can be an ester of a halogenated carboxylic acid, a halogenated ester of a carboxylic acid, or a halogenated ester of a halogenated carboxylic acid. Examples of the ester include bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, and α, β-dichloroacrylate. Can be mentioned.

Examples of the halogenated amide compound include chloroacetamide, bromoacetamide, dichloroacetamide,
Examples thereof include trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide, N-chlorosuccinimide and N-bromosuccinimide.

Examples of halogenated sulfone compounds include US Pat.
The compounds described in the specifications of 3042515 and 3502476 can be mentioned, and the most typical example is phenyltribromomethylsulfone.

Among the halogen compounds, a halide having one or more halogen atoms bonded to the same carbon atom is preferable,
Particularly preferred is a halide having three halogen atoms in one carbon atom. The organic halogen compounds may be used alone or in combination of two or more.

The amount of the organohalogen compound used in the present invention is in the range of 0.001% by weight to 5% by weight of the solid content of the photopolymerizable composition.

More preferably, it is 0.005% by weight to 1% by weight.

Representative leuco dyes that can be used in the present invention include the following. Bis (p-dibutylaminophenyl)-[p- (2-cyanoethyl) methylaminophenyl] methane, bis (p-dimethylaminophenyl)
Aminotriarylmethanes such as -2-quinolylmethane, tris (p-dipropylaminophenyl) methane, 3,
6-bis (diethylamino) -9-phenylxanthene, 3-amino-6-dimethylamino-2-methyl-9
Aminoxanthenes such as-(o-chlorophenyl) xanthene, aminothio such as 3,6-bis (diethylamino) -9- (o-ethoxycarbonylphenyl) thioxanthene, 3,6-bis (dimethylamino) thioxanthene Amino-9, such as xanthenes, 3,6-bis (diethylamino) -9,10-dihydro-9-phenylacridine, 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine. Aminophenoxazines such as 10-dihydroacridine, 3,7-bis (diethylamino) phenoxazine, aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine, 3,7-bis (diethylamino) Aminodihydrophenazines such as -5-hexyl-5,10-dihydrophenazine and amino phosphine such as bis (p-dimethylaminophenyl) anilinomethane Aminohydrocinnamic acids such as phenylmethanes, 4-amino-4'-dimethylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester, 1- (2-naphthyl) -2-phenyl Hydrazines such as enylhydrazine,
Amino-2,3-dihydroanthraquinones such as 1,4-bis (ethylamino) -2,3-dihydroanthraquinone, N, N
-Diethyl-p-phenethylaniline and other phenethylanilines, 10-acetyl-3,7-bis (dimethylamino) phenothiazine and other basic NH group-containing acyl derivatives of leuco dyes, tris (4-diethylamino) -O-tolyl) ethoxycarbonylmethane and the like, but having no oxidizable hydrogen, but oxidizable to a color-forming compound, leuco-like compound, leucoin digoid dye, U.S. Pat. Nos. 3,042,515 and 3,042,517. Organic amines that can be oxidized to such a colored form. Representative compounds of this type include: 4,4'-
Ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4'-methylenediaminetriphenylamine, N-vinylcarbazole.

The amount of the leuco dye used in the present invention is in the range of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the photopolymerizable composition.

Examples of the dyes used in the present invention include Victoria Pyur Blue, Arachite Green Oxalate, Diamond Green Sulfate, Auramine Base, Crystal Violet, Fuchsin, Oleozol Fast Blue, Methyl Orange, and Acid Oleyt.

The photopolymerizable resin composition of the present invention is dissolved or dispersed in a solvent to form a coating solution, which is coated on a support by an appropriate method,
It is common to dry and, if necessary, overlay a protective film thereon as the imaging element.

Examples of the solvent for the coating liquid include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone. , Ethyl acetate, butyl acetate, acetic acid-n-amyl, methyl formate, ethyl propionate, dimethyl phthalate, ethyl benzoate, etc., aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene, carbon tetrachloride, etc. , Halogenated hydrocarbons such as trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene, etc., tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethers such as 1-methoxy-2-propanol, dimethylformamide, and the like dimethyl sulfoxide.

The material used as the above-mentioned support is required to have good light transmittance and have a uniform surface. Specifically, polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester,
Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer,
Various plastic films such as polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene can be used. Further, a composite material composed of two or more of these can also be used.

A support having a thickness of 5 to 150 μm, preferably 10 to 50 μm is generally used, but a support other than the above can be used.

The thickness of the layer of the photopolymerizable composition provided on the support is set so as to perform a desired function of an image finally formed, but is generally 5 to 100 μm. It is in the range, and preferably in the range of 10 to 80 μm.

The photopolymerizable composition of the present invention is used by coating it on a support, and if necessary, a protective film can be provided on the photopolymerizable composition layer. The protective film can be appropriately selected from those used for the support and paper such as paper laminated with polyethylene, polypropylene or the like. Thickness is 5
100 μm is generally used, and 10 to 50 μm is more preferable. At that time, it is necessary that the adhesive force A between the photopolymerizable composition layer and the support and the adhesive force B between the photopolymerizable composition layer and the protective film be A> B. Specific examples of the support / protective film combination include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyamide (nylon 6) / polyethylene,
Examples include polyvinyl chloride / cellophane and polyimide / polypropylene.

In addition to the method of selecting the support and the protective film from mutually different ones as described above, surface treatment of at least one of the support and the protective film may satisfy the above adhesive force relationship. it can. The surface treatment of the support is generally performed in order to enhance the adhesive force with the photopolymerizable composition layer, for example, coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, There are high-frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, laser beam irradiation treatment and the like.

Further, the surface treatment of the protective film is generally performed in order to reduce the adhesive force with the photopolymerizable composition layer, contrary to the surface treatment of the above-mentioned support, such as polyorganosiloxane and fluorine. There is a method of providing a modified polyolefin, polyfluoroethylene or the like as an undercoat layer.

Drying after application is generally 30 ° C to 150 ° C, especially 50 ° C to 1
It is better to carry out at 20 ° C for 1 to 30 minutes.

When the above-mentioned image forming material has a protective film, it is peeled off to expose the surface of the photopolymerizable composition layer, and this is laminated on the desired cleaned substrate surface under pressure.

As the substrate, various ones are used according to the purpose of use of the present invention, for example, a plastic film having a different adhesive force to the photopolymerizable layer from that used for the support, paper,
Wood, metal plate, glass plate, etc. are used. In particular, when the present invention is used as a resist for producing a printed wiring, a thin layer of a metal such as copper, aluminum or silver is formed on or under the plastic plate, or a hole formed through the plastic plate, that is, an inner wall of a through hole. A printed wiring board adhered to the surface or adhered by plating, or a substrate provided with a thin film of metal on a thin plastic film by vapor deposition or plating is used, and the present invention is further applied to a printing plate. When used, an aluminum plate, a plastic film provided with an aluminum layer, or the like is used. In this case, it is preferable that the metal surface of aluminum or the like is subjected to a treatment such as a silicate treatment or anodization.

Lamination of the photopolymerizable composition layer on these substrates is performed at room temperature (15-
30 ℃) or under heating (30-180 ℃),
It is particularly preferable to carry out at 80 to 140 ° C.

The photosensitive layer and support thus laminated on the substrate are then imagewise exposed through a transparent support, generally through a document. As a light source, an electromagnetic wave that transmits through a transparent support and is active with respect to the photopolymerization initiator used, and has a wavelength of 31
A light source that emits ultraviolet-visible light in the range of 0 to 700 nm, more preferably 350 to 500 nm is used. For example, a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent tube for copying, etc. are used. In addition to this, exposure may be performed using a laser beam, an electron beam, an X-ray, or the like.

After imagewise exposure, the transparent support is removed and an appropriate developing solution,
For example, the unexposed portion is eluted with an alkaline aqueous solution or an alkaline aqueous solution containing an organic solvent to obtain a photocured image on the substrate.

After image formation, desired processing can be performed if necessary. For example, when making a printed wiring board, the exposed metal is etched using a known etching solution such as an aqueous solution of copper chloride or an aqueous solution of ferric chloride, or a known plating solution such as copper pyrophosphate or copper sulfate. Can be used to make plating on the exposed metal.

Further, the photo-polymerizable composition of the present invention may be dissolved in the above-mentioned solvent to directly apply the solution on a substrate using a spinner, a wheeler or the like, followed by drying to prepare a photoresist.

The photopolymerizable resin composition of the present invention is particularly preferably used for producing a printed wiring board, and further for a wide range of purposes such as production of a flat plate or a relief printing plate, production of a relief mold, optical duplication, photography and the like. Can be used.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. "Parts" means "parts by weight" unless otherwise specified.

Examples 1 to 4 The materials shown below were mixed to prepare a uniform solution (hereinafter, referred to as mother liquor).

A 35 wt% solution of methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate copolymer (molar ratio = 55 / 28.8 / 11.7 / 4.5: weight average molecular weight 90,000) (solvent is methyl ethyl ketone / 1 = methoxy-2
-Propanol = 2/1 (weight ratio)) 42.9 parts Polypropylene glycol diacrylate (average molecular weight
822) 6.5 parts Tetraethylene glycol dimethacrylate 1.5 parts p-toluenesulfonamide 0.5 part 2- (o-chlorophenyl) -4,5-diphenylimidazole 25 wt% solution of dimer (Hodogaya Chemical Co., Ltd.)
B-CIM, solvent is toluene / methanol = 2/1 (weight ratio)
Solvent) 2.0 parts 4,4-bis (diethylamino) benzophenone 0.04 part Benzophenone 1.0 part Tribromomethylphenyl sulfone 0.05 part Leuco Crystal Violet 0.02 part Malachite Green Oxalate (1% methanol solution)
1.625 parts To each of the above mother liquors, a heterocyclic compound (1 to 6 in Table 1) corresponding to the compound (I) or (II) of the present invention is shown in Table 2.
The amounts shown in Examples 1 to 4 were added.

After further stirring and dissolving, each coating solution was coated on a 25 μm polyethylene terephthalate plate support and dried at 100 ° C. for 2 minutes to obtain a light-sensitive material having a coating film with a thickness of about 40 μm. 120 on a copper clad laminate (substrate) with this sensitive material cleaned.
Laminate at ℃, line width / space width = 1/3, line width 30, 40, 50, 60 and 70Km through negative original 5Kw
Using an ultra-high pressure mercury lamp (HMW-6N manufactured by Oak Co., Ltd.),
The whole surface was exposed for a second. 15 minutes after exposure, spray development with 1% sodium carbonate aqueous solution (30 ° C) for 40 seconds (spray pressure 2 kg / cm
² ) I did.

The obtained resist pattern was observed with an optical microscope, and the line width of the thinnest line in close contact with the substrate was recorded.

The red discoloration was evaluated as follows. After laminating the coated film on the surface adjusted substrate by the above method, 30 ℃ 80% RH
The sample was placed in a thermo-hygrostat of No. 3 and developed after 5 days under the above conditions.
The redness of the exposed copper surface was visually compared. Note that the red discoloration tends to increase with time.

For the mates, line width / space width = 1/1, line width = 1
A pattern in which a 00 μm original was printed and developed was used. This was degreased (PC-455 manufactured by Meltex Co .; 25%, 40 ° C, 3
After that, ammonium persulfate aqueous solution (12%, 30 ° C,
40 seconds), washed with 10% sulfuric acid, and plated with copper sulfate.
After peeling the resist with a 2% caustic soda aqueous solution (50 ° C.), a Mylar tape was attached to the obtained copper plating pattern and rapidly peeled off to perform a peeling test.

Table 1 shows the structure of the heterocyclic compound used in Table 1, and Table 2 shows the evaluation results.

Comparative Examples 1 to 12 Sensitive materials were prepared in the same manner as in Examples except that the kind or / and amount of the heterocyclic compound added to the mother liquor shown in Examples was changed to those shown in Comparative Examples 1 to 12 in Table 2. Was made and the same evaluation was performed. The results are shown in Table 2.

As shown in Table 2, the use of the compound of the present invention (I) alone has a great effect on the improvement of adhesion, but the prevention of red discoloration is insufficient. (Comparative Examples 2 to 5) Compounds of the present invention (II) and their analogs Nos. 7 and 8
Although the compound (1) has an effect of suppressing red discoloration when used alone, adhesion and peeling off are poor. (Comparative examples 6-10).

Adhesion for the first time by the combination of the present invention (I) and (II),
It was possible to satisfy all of the prevention of red discoloration and the peeling of the ink (Examples 1 to 4), and none of the other combinations (Comparative Examples 11 and 12).

(Effects of the Invention) By using the photopolymerizable composition containing the combination of the compounds (I) and (II) of the present invention, it is possible to obtain a photoresist which is excellent in adhesion and is free from red discoloration and peeling.

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Claims (1)

[Claims] 1. A photopolymerizable composition comprising at least (1) to (4). (1) Non-gaseous ethylenically unsaturated compound having at least two ethylenically unsaturated groups and capable of forming a polymer (2) Thermoplastic organic polymer binder (3) Activated by actinic rays Photopolymerization initiator system (4) 0.001 to 0.1% by weight based on the solid content of the photopolymerizable composition
0.01 to 0.5 wt% of the general formula (II) based on the solid content of the heterocyclic compound represented by the general formula (I) and the photopolymerizable composition
A heterocyclic compound represented by the general formula (I) R ₁ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an amino group, or a substituted amino group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted alkyl group, Represents an aryl group or an aralkyl group, R ₄ and R ₅ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or an aralkyl group, and represent pyrrolidine, piperidine, morpholine or an N-substituted piperazine nucleus together with an N atom. You may form. X is an oxygen atom or a sulfur atom [R ₆ represents a hydrogen atom, an alkyl group or an aryl group. ] And Y represents an oxygen atom or a sulfur atom. General formula (II) R _{7 to} R ₁₁ : represent a hydrogen atom, an alkyl group, or an aryl group.