KR0169085B1 - Photopolymerizable composition - Google Patents

Abstract

The photopolymerizable composition contains at least a photopolymerization initiator and an addition polymerizable compound. Said photoinitiator is at least (A) sulfide type compound (B) benzophenone type compound. (C) Alkylamino benzophenone type compound. (D) 2,4,5-triarylimidazolyl dimer, and (E) triarylmethaneroic dye. Preferred photopolymerization initiators also contain p- (dialkylamino) benzoic acid alkyl esters. The photopolymerizable composition is used as a photoresist for coating. The photopolymerizable composition for photoresist contains a thermoplastic polymer, preferably an alkali soluble polymer. Alkali-soluble polymers contain non-styrene polymers and styrene polymers.

Description

[Name of invention]

Photopolymerizable composition

[Technical Field]

The present invention relates to photopolymerizable compositions useful as coating materials, photoresists and the like.

Background Technology

Background Art Conventionally, organic solvent-containing coating compositions and aqueous coating compositions have been known as coating compositions applied to species, plastic films, sheets, metals and the like. Films formed by these coating compositions have usually been formed by heat curing, but since energy efficiency is insufficient and the curing speed is low, a great deal of heat energy is required for heat curing. Moreover, in order to raise productivity, it is necessary to lengthen a heat hardening line.

On the other hand, the photopolymerizable composition which is high in energy efficiency and productivity, excellent in the characteristic of a cured film, and superposed | polymerized-cured by light irradiation, such as an ultraviolet-ray, is known as a coating composition. Photopolymerizable compositions of this kind usually contain an addition polymerizable compound having at least one ethylenically unsaturated bond and a photopolymerization initiator.

Moreover, the photopolymerizable composition is widely used also as a printed wiring board, a printed board, and the photoresist for metal relief image formation. This type of photopolymerizable composition usually contains an addition polymerizable compound having an α, β-ethylenically unsaturated bond, a photopolymerization initiator, and a thermoplastic polymer. The photopolymerizable composition can be used in a liquid phase, but is widely used in the form of a photosensitive film in which a photosensitive layer made of a photopolymerizable composition is interposed between a light transmissive base film and a protective film in view of workability and environmental pollution. It is used. When producing a printed wiring board, this photosensitive film peels a protective film, Usually, a base film is interposed in the board | substrate, such as a copper clad laminated board, through a photosensitive layer, and is active through a predetermined pattern mask etc. The exposure part is hardened by exposing to light.

Such photopolymerizable compositions are required to be excellent in photopolymerization. The photopolymerization rate of the photopolymerizable composition largely depends on the type of photopolymerization initiator. As a conventional photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl, etc. are known. Moreover, as a photoinitiator which is more excellent in photopolymerization than the said various photoinitiators, the photoinitiator which combined benzophenone and N, N'-bis (diethylamino) benzophenone, a lophine dimer, a lophine dimer, and a leukotriphenyl Photopolymerization initiators (Japanese Patent Publication Nos. 45-37, 377) made of methane dyes and the like have been proposed. However, photopolymerizable compositions containing these photopolymerization initiators do not yet have sufficient photopolymerization rates.

In the case where the thermoplastic polymer in the photoresist composition for photoresist is a solvent-soluble polymer or an alkali-soluble polymer, after curing the exposed portion, the non-exposed portion is made of an organic solvent or an aqueous alkali solution by utilizing the solubility difference between the exposed portion and the non-exposed portion. The resist image is formed by dissolving and developing with the developed solution. Moreover, when a thermoplastic polymer is chlorinated polyethylene etc., the resist image is formed by the peeling phenomenon which peels and develops a base film using the adhesive difference of the exposure part of a photosensitive film with a non-exposed part with respect to a board | substrate. Therefore, what is excellent in developability and the resolution is calculated | required as said photopolymerizable composition. In addition, when developing with a developing solution, it is also required to have excellent resistance to the developing solution. In addition, as the developer, an organic solvent-type developer such as 1,1,1, -trichloroethane is known, and this developer is accompanied by problems such as contamination of the working environment, the surrounding environment and an increase in manufacturing cost. Developers consisting of aqueous alkali solutions containing basic compounds such as these are widely used.

After the resist image is formed by the above development, in the case of producing a printed board, the resist image is used as a mask to perform an etching process, a plating process, or the like to form a pattern corresponding to the resist image, and the resist image is a release liquid Peeling is removed. Therefore, the resist image is required to be excellent in adhesion to the substrate, and to be peeled off quickly by the stripping liquid, as well as those exhibiting excellent resistance to the etching liquid and the plating liquid. These properties largely depend on the composition of the photopolymerizable composition, and resist images exhibiting excellent resistance to etching liquids and plating liquids generally have very high resistance to peeling liquids, but lack peelability. In particular, since the photopolymerizable composition capable of alkali development contains a thermoplastic polymer having an activated carboxyl group, a long time is required for peeling when the resist image is peeled off with a strong alkali aqueous solution such as sodium hydroxide or potassium hydroxide. Therefore, not only productivity of a printed wiring board etc. falls, but a metal substrate, especially copper foil of an operating red-plated board, produces a blackish so-called [alkali soot] by aqueous alkali solution, and adversely affects the subsequent process.

In addition, in the photosensitive film, it is required that the photopolymerizable composition does not leak at the end of the anti-cold flow, that is, the photosensitive film preserved in the wound state.

US Patent No. 3,930,865 discloses a photopolymerizable composition in which a polymerizable monomer having a carboxyl group, a methacrylic acid ester having an alkyl group of 4 or more carbon atoms, and a thermoplastic polymer composed of 1-35% by weight of a styrene monomer are disclosed. . Japanese Patent Application Laid-Open No. 58-12, 577 discloses 1--40% by weight of a polymerizable monomer having a carboxyl group and 35-83% by weight of methacrylate ester having an alkyl group having 6 to 12 carbon atoms and styrene. A photopolymerizable composition containing a thermoplastic polymer composed of 3-25% by weight of a monomer is disclosed. Since these photopolymerizable compositions combine styrene-based monomers with methacrylic acid esters as constituents of the thermoplastic polymer, they have excellent alkali developer resistance and etch resistance and exhibit some degree of low temperature flow resistance, but still have a high resolution. Not full yet.

Japanese Patent Publication Nos. 54-25 and 957 also disclose 15-40 wt% of a polymerizable monomer having a carboxyl group and 15-45 wt% of a methacrylic ester and an acrylic ester having an alkyl group having 1 to 6 carbon atoms. A photopolymerizable composition containing a polymer composed of% and 40-60% by weight of a styrene monomer is disclosed. This photopolymerizable composition is excellent in cryogenic flow resistance than the thermoplastic polymer, but the resolution is not sufficient as described above.

Each component constituting such a photopolymerizable composition has an enormous influence on photopolymerizability, developability, resolution, resistance of the resist film and peeling properties, and conventional photopolymerizable compositions do not yet have sufficient characteristics.

Accordingly, an object of the present invention is to provide a photopolymerizable composition excellent in photopolymerization.

Another object of the present invention is to provide a photopolymerizable composition capable of peeling a resist film in a short time.

It is still another object of the present invention to provide a photopolymerizable composition which is capable of alkylation and is excellent in alkylli developer, etch resistance and plating solution resistance.

Another object of the present invention is to provide a photopolymerizable composition having excellent resolution and low temperature flow resistance.

[Initiation of invention]

The present invention provides a photopolymerizable composition containing at least a photopolymerization initiator and an addition polymerizable compound in a liquid or solid at room temperature and normal pressure, wherein the photopolymerization initiator contains at least the following components (A) to (E). .

(A) sulfide compounds represented by the general formula [I]

(In formula, R <^1> , R <^2> and R <^3> is the same or different from each other, and is a group selected from the group which consists of a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group, and an aralkyl group. 1 and n are integers of 1-5, m represents an integer of 1-4).

(B) The benzophenone type compound which may have a substituent selected from the group which consists of an aryl group, an alkoxycarbonyl group, and an alkoxy group which may have a halogen atom, an alkyl group, and a substituent.

(C) Alkylamino benzophenone type compound which may have a substituent selected from the group which consists of a halogen atom, an alkyl group, and an aryl group which may have a substituent, an alkoxycarbonyl group, and an alkoxy group.

(D) 2,4,5-triarylimidazolyl dimer which may have a substituent, and

(E) triarylmethane leuco dye

Preferred photopolymerization initiators contain p- (dialkylamino) benzoic acid alkyl esters.

The present invention also provides a photopolymerizable composition containing the photopolymerization initiator, an addition polymerizable compound which is a liquid or a solid at room temperature and atmospheric pressure, and a thermoplastic polymer. This photopolymerizable composition is useful as a photoresist. A preferable addition polymeric compound contains the phthalic acid derivative which has a (meth) acryloyl group, for example. Preferred addition polymerizable compounds include phthalic acid derivatives, (meth) acrylates having three (meth) acryloyl groups in the molecule, polyoxyalkylenedi (meth) acrylates, and di (meth) acryl having bisphenol A skeletons. Contains the rate.

Preferred thermoplastic polymers are alkali-soluble polymers, in particular thermoplastic polymers having an acid value of 100-350. Thermoplastic polymers are roughly classified into non-styrene polymers and styrene polymers. Preferred non-styrene polymers are copolymers with (a) 15-40% by weight of acidic addition polymerizable monomers having carboxyl groups, (b) (meth) acrylates having phenoxy groups, and (c) non-acidic addition polymerizable monomers. to be.

Preferred polymers are copolymers with 15-40% by weight of acidic addition polymerizable monomers having carboxyl groups, 1-35% by weight of styrenic monomers, 84-25% by weight of acrylic esters and methacrylic esters.

Detailed description of the invention

The photoinitiator contains the sulfide type compound represented by general formula [I] as a component (A). In the sulfide compound represented by the general formula [I], examples of the alkyl groups of the substituents R ¹ , R ^2, and R ³ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and jade. Til group etc. are illustrated.

As an aryl group, a phenyl, naphthyl, anthryl group, etc. are illustrated.

Examples of the substituent for the alkyl group include halogen atoms such as fluorine, chlorine and bromine, alkoxy groups such as hydroxy group, methoxy, ethoxy and propoxy group, alkoxy such as carboxyl group, methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl group Alkyl amino groups, such as a carboxyl group, an amino group, a dimethylanino, and a diethylamino group, a nitro group, a cyano group, etc. are illustrated. As a substituent of an aryl group, the said alkyl group and the substituent of the said alkyl group are illustrated.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, heptyloxy, heptyloxy, octyloxy and the like.

Examples of the aralkyl group include benzyl, phenethyl, 3-phenylpropyl, benzhydryl group and the like.

Substituents R ¹ , R ² and R ³ may be substituted with appropriate positions of the benzene ring, or may be substituted with the same or different kinds of substituents in the same benzene ring.

Preferred groups of R ¹ and R ² are each a hydrogen atom. R ³ is a lower alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

Among the sulfide compounds represented by the general formula [I], particularly preferred compounds include, for example, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'ethyldiphenylsulfide and 4-benzoyl- 4'-propyldiphenyl sulfide, 4-benzoyl-4'-isopropyldiphenyl sulfide, 4-benzoyl-4'-butyl diphenyl sulfide, etc. are illustrated. These sulfide compounds can be used alone or in combination of two or more.

In addition, the photoinitiator contains at least one benzophenone type compound which may have a substituent as a component (B). As said substituent, the aryl group, the alkoxy group, and the alkoxycarbonyl group which may have the halogen atom, alkyl group, and substituent which were illustrated above are illustrated. Preferred benzophenone compounds are benzophenones. At least one of these benzophenone compounds is used.

The benzophenone-based compound is usually used in a proportion of 50-500 parts by weight, preferably 100-400 parts by weight, more preferably 200-350 parts by weight, based on 100 parts by weight of the compound represented by the general formula [I]. When the amount of the benzophenone-based compound is out of the above range, the photosensitivity is lowered.

As a substituent of the alkylamino benzophenone type compound contained as a component (C) in a photoinitiator, the aryl group, the alkoxy group, and the alkoxycarbonyl group which may have the halogen atom, alkyl group, and substituent which were illustrated above are illustrated. Examples of the alkylaminobenzophenone compounds include 4-methyl-4'-diethylaminobenzophenone, 4-methoxy-4'-diethylaminobenzophenone, 4,4'-bis (methylamino) benzophenone , 4-methylamino-4'-ethylaminobenzophenone, 4-diethylaminobenzophenone and the like. Preferred alkylaminobenzophenone compounds are 4, 4'-bis (methylamino) benzophenone. As 4, 4'-bis (alkylamino) benzophenone, it is 4, 4'-bis (dimethylamino) benzophenone, 4-dimethylamino-4'- diethylamino benzophenone, 4, 4'-bis, for example. (Diethylamino) benzophenone, 4, 4'-bis (dipropylamino) benzophenone, 4, 4'-bis (diisopropylamino) benzophenone, 4, 4'-bis (dibufilamino) benzophenone , 4, 4'-bis (diisobutylamino) benzophenone, 4, 4'-bis (di-t-butylamino) benzophenone and the like. Among these compounds, 4, 4'-bis (dimethilamino) benzophenone and 4, 4'-bis (diethylamino) benzophenone are particularly preferable.

At least 1 type of alkylamino benzophenone type compound is used.

The ratio of the alkylaminobenzophenone compound to 100 parts by weight of the compound represented by the general formula [I] is generally 5-250 parts by weight, preferably 10-200 parts by weight, more preferably 20-175 parts by weight. . When the amount of the alkylamino benzophenone compound is outside the above range, the photosensitivity is lowered.

In addition, the photoinitiator contains 2,4,5-triaryl imidazolyl dimer which may have a substituent as a component (D). This 2,4,5-triaryl imidazolyl dimer is represented by the following general formula [II].

In formula, Ar <^1> , Ar <^2> and Ar <^3> represent the aryl group which may have a substituent.

As said substituent, the halogen atom and the alkoxy group which were illustrated above, and alkylthio groups, such as methylthio and an ethylthio group, are illustrated.

As 2,4,5-triaryl imidazolyl dimer represented by general formula [II], it is 2,2 ', 4,4', 5,5'-hexaphenyl bisimidazole, 2,2 ', for example. -Di (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (p-chlorophenyl) -4,4', 5,5'-tetraphenyl Bisimidazole, 2,2'-di (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (p-chlorophenyl) -4,4' , 5,5'-tetra (m-methoxyphenyl) bisimidazole, 2,2'-di (p-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) bis Imidazole, 2,2'-di (o-fluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (p-methoxyphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-di ( 2,4-dimethoxyphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2', 4,4 ', -tetra (p-methoxyphenyl) -5,5'- Diphenylbisimidazole, 2,2'-di (p-methylthiophenyl) -4,4 ', 5,5'-tetraphenyl ratio It is already examples include imidazole. At least 1 type of 2,4,5-triaryl imidazolyl dimer represented by the said General formula [II] is used.

The 2,4,5-triarylimidazolyl dimer is usually used in an amount of 50-400 parts by weight, preferably 100-300 parts by weight, relative to 100 parts by weight of the compound represented by the general formula [I]. If the amount of 2,4,5-triarylimidazolyl dimer is out of the above range, the photosensitivity is not sufficient.

In addition, a photoinitiator contains as a component (E) a triaryl methane leuco dye. It is very suitable that this triarylmethaneco dye has a substituted amino group, especially at least one dialkyl amino group, and functions as a free radical generator. As a triaryl methane leuco dye, for example, tris (4-N, N-diethylamino-o-tolyl) methanetritate, bis (4-N, N-diethylamino-o-tolyl) thienyl methane , Bis (4-N, N-diethylamino-o-tolyl) benzylthiophenylmethane, leuco malachite green (C. I. Basic green 4), leuco crystal violet (C. I. Basic violet 3), brilliant green (C. I. Basic green 2), Victoria Green 3B (C. I. Basic green 4), Acid Green GG (C. I. Basic green 1), Methyl violet (C. I. Basic violet 1), Rose Aniline (C. I. Basic violet 14) and the like. These triarylmethane leuco dyes can be used as organic acid salts such as hydrochloride, sulfate and the like, mineral salts, p-toluene sulfonate. Triaryl methane leuco dye can use at least 1 sort (s).

The triarylmethaneroic dye is usually used in an amount of 10 to 70 parts by weight, preferably 25 to 55 parts by weight, relative to 100 parts by weight of the compound represented by the general formula [I]. When the amount of the triarylmethane leuco dye is outside the above range, the photosensitivity is degraded.

In order to further enhance the photopolymerization of the photopolymerizable composition containing the photopolymerization initiator comprising (A) (B) (C) (D) and (E), the photopolymerization initiator is (F) p-(dialkylamino) benzoic acid. It is preferable to contain an alkyl ester.

The p-(dialkylamino) benzoic acid alkyl ester is represented by the following general formula [III].

In the formula, R ⁴ , R ⁵ and R ⁶ are the same as or different from each other and represent a lower alkyl group.

As a lower alkyl group, linear or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl group, are illustrated, for example. Among these alkyl groups, alkyl groups having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, are preferable.

Preferred p- (dialkylamino) benzoic acid alkyl esters are, for example, methyl p- (dimethylamino) benzoic acid, ethyl p- (dimethylamino) benzoic acid, p- (dimethylamino) benzoic acid propyl, p- (dimethylamino) benzoic acid Isopropyl, p-(N-methyl-N-ethylamino) methyl benzoate, p-(N-methyl-N-ethylamino) ethyl benzoate, p-(diethylamino) methyl benzoate, p-(diethylamino) Ethyl benzoate, p-(diethylamino) benzoic acid propyl, p-(diethylamino) benzoic acid isopropyl, p-(dipropylamino) benzoic acid methyl, p-(dipropylamino) benzoic acid ethyl, p-(dipropylamino ) Benzoic acid propyl, p- (dipropylamino) benzoic acid isopropyl, and the like. One or two or more p- (dialkylamino) benzoic acid alkyl esters represented by General Formula [III] can be used.

The p- (dialkylamino) benzoic acid alkyl ester is usually used in an amount of 25-200 parts by weight, preferably 50-100 parts by weight, based on 100 parts by weight of the sulfide compound represented by the general formula [I]. . When the amount of p-(dialkylamino) benzoic acid alkyl ester is out of the above range, the polymerization rate of the photopolymerizable composition is likely to decrease.

The photopolymerizable composition containing the photopolymerization initiator consisting of the above components (A)-(E) or (A)-(F) exhibits a large photopolymerization rate, and the excitation and energy transition of the photopolymerization initiator by light irradiation proceed smoothly. It is assumed that the addition polymerizable compound is radically polymerized efficiently.

Moreover, the said photoinitiator may contain substituted or unsubstituted polynuclear quinones, benzoin, benzoin ether, substituted or unsubstituted "thioxanrons, and another photoinitiator as needed. Substituted or unsubstituted polynuclear quinones are, for example, 2-methylanthraquinone, 2-ethylanthraquinone, 2-propylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, benz [a] anthraquinone, benz [b] anthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 3 -Chloro-2-methylanthraquinone, 1,4-naphthaquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthaquinone, 2,3-dichloronaphthaquinone, 7,8,9,10 -Tetrahydronaphthacequinone, etc. are illustrated. As benzoin and benzoin ether, benzoin, methyl benzoin, ethyl benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. are illustrated, for example. As substituted or unsubstituted thioxanthone, it is thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2, 4- dimethyl, for example. Thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dibutyl thioxanthone, etc. are illustrated. As another photoinitiator, oxime esters, such as benzyl, (alpha), (alpha)-diethoxy acetphenone, and benzophenone oxime acetate, etc. are illustrated.

Moreover, it is useful to use the said photoinitiator in combination with appropriate amount of aliphatic or aromatic amines. Examples of the aliphatic or aromatic amines include 2-mercaptobenzoxazole, ethanolamine, diethanolamine, triethanolamine, diethylaninoethanol, N-methyl diethanolamine, N-ethyl diethanolamine, and Nn-. Butyldiethanolamine, allylthiourea, N, N-diethylglycine, aniline, N-methylaniline, N, N-diethylaniline, N-ethyl morpholine, etc. are illustrated.

The photopolymerizable compositions of the present invention are roughly classified for coating and photoresist.

Next, the photopolymerizable composition for coating is demonstrated.

The photopolymerizable composition for coating contains at least the photopolymerization initiator and the addition polymerizable compound. The addition polymerizable compound is not particularly limited as long as it is a liquid or solid at room temperature and normal pressure, and a compound having at least one α, β-ethylenically unsaturated group in a molecule. In view of photopolymerization, compounds having two or more acryloyl groups and / or methacryloyl groups in the molecule are preferable. Examples of the acrylate having two acryloyl groups in the molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, Propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, Ethylene of bisphenol A such as 1-6-hexanediol diacrylate, 2,2-bis (4-acryloyldiethoxyphenyl) propane, and 2,2-bis (4-acryloylpentaethoxyphenyl) propane Diacrylates of oxide adducts, 2,2-bis (4-acryloyldipropoxyphenyl) propane, 2,2-bis (4-acryloylpentapropoxy Diacrylates of propylene oxide adducts of bisphenol A, such as nil) propane, diacrylates of ethylene oxide adducts of hydrogenated bisphenol A, diacrylates of propylene oxide adducts of hydrogenated bisphenol A, N, N'-methylenebisacrylamide, N, N'-benzylidene acrylamide etc. are illustrated.

As an acrylate which has three or more acryloyl groups in a molecule | numerator, for example, glycerol triacrylate, a trimethylol propane triacrylate, a trimethylol ethane triacrylate, a pentaerythritol triacrylate, a pentaerythritol triacryl Elate, dipentaerythritol hexaacrylate, etc. are illustrated.

As methacrylate which has a 2 or more methacryloyl group in a molecule | numerator, the methacrylate corresponding to the said acrylate is illustrated.

The addition polymerizable compound having two or more acryloyl groups and / or methacryloyl in the molecule may be an oligomer, and examples of the oligomers include epoxy acrylate, oligoester acrylate, urethane acrylate, and the like. The methacrylate corresponding to is illustrated.

1 type (s) or 2 or more types can be used for these addition polymeric compounds.

The photopolymerization initiator is usually used in an amount of 0.1-30 parts by weight, preferably 1-25 parts by weight, based on 100 parts by weight of the addition polymerizable compound. When the amount of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerization property is lowered. When the amount of the photopolymerization initiator is more than 30 parts by weight, the photopolymerizable composition is deteriorated in stability.

Further, the photopolymerizable composition for coating may be an organic polymer such as acrylic polymer, styrene polymer, polyvinyl acetate, ethylene-vinyl acetate, polyvinyl chloride, polyvinyl chloride-vinyl acetate copolymer, chlorinated polyethylene, chlorinated polypropylene, Vinylidene chloride polymers, polyesters, polyamides, polyurethanes, polyvinyl acetals, alkyd resins, phenolic resins, epoxy resins, cellulose-based polymers such as cellulose acetate and nitrated cotton, styrene-butadiene copolymers, styrene-acrylonitrile Synthetic rubber, such as a copolymer, chlorinated rubber, and cyclized rubber, or natural rubber may be contained. The organic polymer may be an alkali-soluble polymer having a carboxyl group. The photopolymerizable composition may contain an oil or fat or wax.

The photopolymerizable composition for coating may contain the organic solvent as needed. Examples of the organic solvent include alcohols such as methanol, ethanol and propanol, alicyclic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, acetone and methyl ethyl ketone. Ketones, diethyl ether, ethers such as tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, and the like, and mixed solvents thereof.

In addition, the photopolymerizable composition for coating can also be used as an adhesive.

Next, the photopolymerizable composition for photoresist will be described.

The photopolymerizable composition for photoresists contains the addition polymerizable compound and the thermoplastic polymer of the photopolymerization initiator.

The usage-amount of a photoinitiator is 0.1-30 weight part normally with respect to 100 weight part of thermoplastic polymers, Preferably it is 1-15 weight part. When the amount of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerization property is lowered. When the amount of the photopolymerization initiator is more than 30 parts by weight, the photopolymerizable composition is deteriorated in stability.

The addition polymerizable compound is a liquid or solid at normal temperature and normal pressure, and contains a compound having at least two α, β-ethylenically unsaturated groups in the molecule. The addition polymerizable compound is preferably a compound having two or more acryloyl groups and / or methacryloyl groups in the molecule. Such an addition polymerizable compound imparts excellent photopolymerization property, developer resistance, etching resistance and plating solution resistance to the photopolymerizable composition.

In order to peel a resist film in a short time, it is preferable that an addition polymeric compound contains the compound represented by following General formula [IV] at least as component (1).

Wherein R ⁷ and R ¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ⁸ , R ⁹ are the same or different and represent a straight or branched alkylene group, R ¹¹ is a hydrogen atom, a halogen atom or C1-C10 alkyl group is shown. p and q are each an integer of 1-10, and r represents an integer of 1-20.

In general formula [IV], as an alkylene group of R <^8> and R <^9> , methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, heptamethylene, an octamethylene group, etc. are illustrated. As a halogen atom and an alkyl group of R <^11>, the same halogen atom and alkyl group are mentioned above.

The compound represented by general formula [IV] has the (meth) acrylate which has a terminal carboxyl group of the terminal hydroxyl group of the compound obtained by reaction of the aromatic dicarboxylic acid which may have a substituent, and alkylene oxide or a dihydric alcohol. It is esterified with.

In the compound represented by the general formula [IV], the carbonyl group substituted in the benzene ring is positioned at o-, m- and p- positions of the other carbonyl group relative to one carbonyl group. That is, it is a phthalic acid derivative, an isophthalic acid derivative, and a terephthalic acid derivative. As a preferable compound represented by general formula [IV], the phthalic acid derivative shown in the following table is illustrated, for example.

The compound represented by general formula (IV) as a component (1) can be used as 1 type, or 2 or more types of mixtures.

The compound represented by the formula (IV) is contained in the addition polymerizable compound at least 5% by weight, preferably 10-75% by weight, more preferably 15-20% by weight. When the usage-amount of the compound represented by general formula (IV) is less than 5 weight%, long time is required for peeling of the resist film with a peeling liquid according to the kind of thermoplastic polymer.

An addition polymeric compound is added to the said component (1), ie, the compound represented by General formula (IV), At least any one of the following components (2)-(4), Preferably it is a multiple component, especially a component ( It is preferable to use all the components of 2)-(4) together. The photopolymerizable composition containing the addition polymerizable compound composed of such a combination can peel the resist film in a short time, and at the same time, various required characteristics such as photopolymerization, developability, developer resistance, etch resistance and plating solution resistance To meet the balance.

Component (2): (meth) acrylate having three (meth) acryloyl groups in the molecule

As a (meth) acrylate which has three (meth) acryloyl groups in the molecule | numerator as said component (2), For example, glycerin triacrylate, trimethylol tropan triacrylate, the trimethylol ethane triacrylate, Pentaerythritol triacrylate, the methacrylate corresponding to these, etc. are illustrated. Of these (meth) acrylates, trimethylolpropane tri (meth) acrylate is preferred. Component (2) can be used as one kind or a mixture of two or more kinds.

Component (3): Compound represented by the following general formula [V]

In formula, R <^12> , R <^13> and R <^14> is the same or different, shows a hydrogen atom or a methyl group, and s shows the integer of 7-11.

Examples of the compound represented by the general formula [V] as the component (3) include hepdaethylene glycol diacrylate, octaethylene glycol diacrylate, nonaethylene glycol diacrylate, decaethylene glycol diacrylate, and undeca. Ethylene glycol diacrylate, heptapropylene glycol diacrylate, octapropylene glycol diacrylate, nonapropylene glycol diacrylate, decapropylene glycol diacrylate, undecapropylene glycol diacrylate or the corresponding dimethacrylates The back belongs. Among these compounds, R ¹³ is a hydrogen atom, R ¹² and R ¹⁴ are each a hydrogen atom or a methyl group, and the repeating unit s is preferably diacrylate or dimethacrylate of 8-10. Component (3) can be used as one kind or a mixture of two or more kinds.

Component (4): Compound represented by the following general formula [VI]

In formula, R <^15> , R <^16> , R <^17> and R <^18> are the same or different, represent a hydrogen atom or a methyl group, t and u represent the integer of 1-15.

Examples of the compound represented by the general formula [VI] as the component (4) include 2,2-bis (4-acryloylethoxyphenyl) propane and 2,2-bis (4-acryloyldiethoxy Phenyl) propane, 2,2-bis (4-acryloyltriethoxyphenyl) propane, 2,2-bis (4-acryloyltetraethoxyphenyl) propane, 2,2-bis (4-acrylo) Ilpentaethoxyphenyl) propane, 2,2-bis (4-acryloylpentaethoxyphenyl) propane, 2,2-bis (4-acryloylhexaethoxyphenyl) propane, 2,2-bis ( 4-acryloyloctaethoxyphenyl) propane, 2,2-bis (4-acryloyldecaethoxyphenyl) propane, 2,2-bis (4-acryloyldodecaethoxyphenyl) propane, 2, 2-bis (4-acryloylpentadecaethoxyphenyl) propane, 2,2-bis (4-acryloylpropoxyphenyl) propane, 2,2-bis (4-acryloyldipropoxyphenyl) Propane, 2,2-bis (4-acryloyltrippoxyphenyl) propane, 2,2-bis (4-acryloyltetrapropoxy Phenyl) propane, 2,2-bis (4-acryloylpentapropoxyphenyl) propane, 2,2-bis (4-acryloylhexapropoxyphenyl) propane, 2,2-bis (4-acrylo) Monooctapropoxyphenyl) propane, 2,2-bis (4-acryloyldecapropoxyphenyl) propane, 2,2-bis (4-acryloyldodecapropoxyphenyl) propane, 2,2-bis ( 4-acryloyl pentadecapropoxyphenyl) propane, the methacrylate corresponding to these, etc. are mentioned.

Among the components (4) represented by the general formula [VI], preferred compounds are all of R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , each being a hydrogen atom, repeating unit t is 1-5, and repeating unit u is 1- 5, in particular t is 2-4 and u is 2-4. Component (4) can be used as 1 type or in mixture of 2 or more types.

The ratio of each component (1)-(4) with respect to a thermoplastic polymer can be determined in the range which does not impair photopolymerizability, developability, developer resistance, etc. The ratio of each component (1)-(4) is 5-20 weight part of components (1), 10-40 weight part of components (2), 2-15 weight part of components (3) with respect to 100 weight part of thermoplastic polymers, 5-20 parts by weight of component (4). The preferred ratio of each component (1) to (4) is 5-15 parts by weight of component (1), 10-30 parts by weight of component (2), and 2-10 parts by weight of component (3) based on 100 parts by weight of thermoplastic polymer. And 5-15 parts by weight of component (4).

In addition, the addition-polymerizable compound may contain other compounds which are liquid or solid at room temperature and normal pressure and have at least one α, β-ethylenically unsaturated group in the molecule in a quantitative range that does not impair the properties such as photopolymerization. . Among these compounds, examples of the compound having one α, β-ethylenically unsaturated group in the molecule include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dimethylaminoethyl acrylate and diethylamino acrylate. Acrylic acid and derivatives thereof such as ethyl, acrylamino and N-methylol acrylamino; Methacrylic acid and its derivatives corresponding thereto; Styrene, vinyl ester, etc. are illustrated. As a compound which has an (alpha), (beta)-ethylenically unsaturated group in a molecule | numerator, For example, in said General formula [V], s is 1-6 and s is an addition polymeric compound which is 12 or more; In the general formula [VI], t and u are 16 or more addition polymerizable compounds; An addition polymerization compound in which t and u are 1 or more in the general formula [VI] and the benzene ring is substituted with a cyclohexyl ring; 1,4-butanedioldiacrylate, neopentylglycoldiacrylate, 1-6-hexanedioldiacrylate, or dimethacrylate corresponding thereto; N, N'-methylenebisacryl amide, N, N'-methylenebismethacryl amide, N, N'-benzylidenebisacryl amide, N, N'-benzylidenebismethacryl amide, etc. are illustrated. As a compound which has four or more (alpha), (beta)-ethylenically unsaturated groups in a molecule | numerator, pentaethyltritol tetraacrylate, dipentaerythritol hexaacrylate, the methacrylate corresponding to these, etc. are illustrated, for example. Moreover, the said oligomer, such as an epoxy acrylate and an oligoester acrylate, may be sufficient as the compound which has a 2 or more (alpha), (beta)-ethylenically unsaturated group in a molecule | numerator.

The ratio of the addition polymerizable compound to 100 parts by weight of the thermoplastic polymer is 25 to 80 parts by weight, preferably 30 to 60 parts by weight. When the amount of the addition polymerizable compound is less than 25 parts by weight, the resolution decreases, and when it exceeds 80 parts by weight, the low temperature flow resistance decreases.

The photopolymerizable composition for photoresists of the present invention contains various thermoplastic polymers dropped in a developing manner. For example, when a developing system is peeling phenomenon, as a thermoplastic polymer, chlorinated polyethylene, chlorinated polypropylene, etc. are chlorinated polyolefin; Acrylic polymers such as polymethyl acrylate, ethyl polyacrylate, polymethyl methacrylate, and ethyl polymethacrylate; Vinyl chloride polymers such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers; Vinylidene chloride polymers such as polyvinylidene chloride, vinylidene chloride, acrylonitrile copolymer, vinylidene chloride-acrylic acid ester copolymer, and vinylidene chloride-vinyl acetate copolymer; Polyvinyl acetate; Saturated polyesters; Polyvinyl acetals such as polyvinyl butyral and polyvinyl promal; Polyisoprene; Poly chloroprene; Chlorosulfonated polyolefins such as chlorosulfonated polyethylene and chlorosulfonated polypropylene; Chlorinated rubber and the like. Preferred peeling phenomena are thermoplastic polymers, chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate saturated polyester. These thermoplastic polymers may be used alone or in combination of two or more.

As the solvent-developed thermoplastic polymer, in addition to conventional conventional polymers, for example, the polymers exemplified above, cyclized rubber, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, Synthetic rubbers such as butadiene-acrylonitrile copolymers, polyurethanes, styrene-based polymers, styrene-based polymers, and cellulose acetate. Fiber-based polymers, such as nitrocellulose, etc. are illustrated. These thermoplastic polymers can be used 1 type or 2 types.

The thermoplastic polymer in the photopolymerizable composition of the present invention is preferably an alkali-soluble polymer. These alkali-soluble polymers are roughly classified into non-styrene polymers containing no styrene monomer as structural units and styrene polymers containing styrene monomer as structural units, and the appropriate composition of these polymers differs depending on the presence or absence of styrene monomers. Do.

The alkali-soluble polymer may have a suitable acid value within the range in which the resist film is resistant to the etching solution and the plating solution, without impairing the developability, resolution, adhesion to the substrate, and peelability of the resist film. The acid value of the thermoplastic polymer depends on the polymer type. The preferred acid value of the thermoplastic polymer not containing styrene units is 100-350, in particular 125-250, and the acid value of the thermoplastic polymer containing styrene units is 100-350, preferably 125-300. If the acid value of the thermoplastic polymer is less than 100, the composition is also changed depending on the composition of the thermoplastic polymer, but generally developability and resolution are lowered, and if it exceeds 350, resolution is generally lowered.

The alkali thermoplastic polymer contained in the photopolymerizable composition is 5-40% by weight of the acidic addition polymerizable monomer (a) having a carboxyl group, preferably 20-35% by weight and 85-60% by weight of the non-acidic addition polymerizable monomer (b). %, Preferably copolymers with 80-65% by weight. The photopolymerizable composition containing such an alkali-soluble thermoplastic polymer is useful for forming a fine pattern, because the development time is short and the resistance of the resist film to the developer is large.

Examples of the acidic addition polymerizable monomer (a) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, propionic acid, sorbic acid, cinnamic acid, and the like. Among the acidic addition polymerizable monomers (a) having a carboxyl group, methacrylic acid, acrylic acid, and especially a mixture of both are preferable. In addition, dicarboxylic acids, such as maleic acid, can also be used as a half ester or an anhydride.

Thermoplastic polymers containing units of the acidic addition polymerizable monomer (a) essentially have the property of swelling or dissolving in an alkaline liquid. Therefore, non-acidic addition polymerizable monomers (b) such as styrene and its derivatives, acrylic esters or methacrylic esters are used as copolymerization components in order to impart resistance to alkaline developing solutions.

Examples of the styrene monomers include styrene; α-substituted styrenes in which the α-position is substituted with an alkyl group or a halogen atom such as α-methylstyrene, α-chlorostyrene and the like; Substituted styrene in which the hydrogen atom of the benzene ring is substituted, for example, p-methyl styrene, p-ethyl styrene, p-propyl styrene, p-isopropyl styrene, p- (t-butyl) styrene and the like are exemplified. Use

Among the styrene monomers, styrene, α-methylstyrene and the like are preferable.

As acrylic ester, acrylic ester which has a C1-C20 alkyl group etc., for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, acrylate-t-butyl, pentyl acrylate, hexyl acrylate, Heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, phenyl acrylate, undecyl acrylate, dodecyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-phenoxyethyl acrylate and the like are exemplified. Moreover, as methacrylic acid ester, methacrylic acid ester corresponding to the said acrylic acid ester is illustrated. Each of these acrylic esters and methacrylic esters is used one or more.

In particular, a photopolymerizable composition containing an alkali-soluble thermoplastic polymer composed of a copolymer of the base (a)-(c) components as the non-styrene polymer is difficult to swell with an alkali corrosion solution and is useful for imparting etching resistance.

(a) 15-40% by weight of an acidic addition polymerizable monomer having a carboxyl group

(b) the following general formula

Wherein R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ is an alkylene group having 1 to 6 carbon atoms, R ²¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and v is a positive integer of 1-20 At least 5% by weight of the non-acidic addition polymerizable monomer represented by

(c) relational expression

0.25 (QA / Qc) Exp [-eA (eA-eC)] 4.00 [Ⅷ]

Wherein Q and e are the stability and polarity of the monomer defined by the formula of Alfrey-Price, symbol A is an acidic addition polymerizable monomer (a), and symbol C is a non-acidic addition polymerizable monomer. The remainder of the non-acidic addition polymeric monomer which has Q value and e value which satisfy | fill (c).

In the compound represented by general formula [K], as an alkylene group of R <^20> , methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, etc. are illustrated. Examples of the alkyl group and halogen atom of R ²¹ include the same alkyl group and halogen atom as described above.

As a preferable non-acidic addition polymeric monomer (b) among the compounds represented by General formula [i], 2-phenoxypropyl acrylate, 2-phenoxypropyl acrylate, 3-phenoxypropyl acrylate, phenoxyethoxy acrylate , Phenoxy diethoxy ethyl acrylate, Phenoxytriethoxy ethyl acrylate, Phenoxy propoxy propyl acrylate, Phenoxy propoxy propyl acrylate, Phenoxy tripropoxy acrylate, Pethyl acrylate (p-chlorophenoxy) ethyl, Acrylic acid (p -Methylphenoxy) ethyl, 2-methoxyl methacrylate, 3-phenoxypropyl methacrylate, phenoxyethoxyethyl methacrylate, phenoxydiethoxyethyl methacrylate, phenoxymethacrylate Methoxyethyl, methacrylic acid penoxypropoxypropyl, methacrylic acid penoxydipropoxypropyl, methacrylic acid penoxytripropoxypropyl, methacrylic acid penoxytripropoxypropyl, methacrylic acid pen Citric Propoxypropyl, Methacrylic Acid Penoxytripropoxypropyl, Methacrylic Acid (p-crofenoxy) ethyl, Methacrylic Acid (p-chlorophenoxy) ethyl, Methacrylic Acid (p-methylphenoxy ) Ethyl and the like.

The units of these non-acidic addition polymerizable monomers (b) are contained at least 5% by weight, preferably 10-70% by weight in the copolymer.

The acidic addition polymerizable monomer (a) and the non-acidic addition polymerizable monomer (b) having a carboxyl group are copolymerized with the non-acidic addition polymerizable monomer (c) satisfying the above relationship [VIII]. The non-acidic addition polymerizable monomer (c) is composed of at least one of styrene monomer, acrylic ester and methacrylic ester.

When copolymerized with the non-acidic addition polymerizable monomer (c) that satisfies the relation [VIII], when copolymerized with the acidic addition polymerizable (c), the air is uniformly distributed in units of the acidic addition polymerizable monomer (a). Coalescing is obtained and it is excellent in developability. That is, as the acidic addition polymerizable monomer (a) and the non-acidic addition polymerizable monomer (c), the value of Q, which is an index of public synthesis in the formula of Alfrey-Price, is approximated, and the sign of e is reversed. The use of monomers with large differences in absolute values can significantly increase aerial synthesis. Therefore, when the monomer which does not satisfy the said relationship [iii] is used, the copolymer in which the unit of the acidic addition-polymerizable monomer (a) was unevenly distributed will obtain a free polymer, and a developing defect will arise at the time of image development, or it will stand out. If this occurs, the copolymer may precipitate during polymerization.

The non-acidic addition polymerizable monomer (c) is suitably selected according to the properties of the acidic addition polymerizable monomer (a), as proposed by the present applicant first (see Japanese Patent Laid-Open Nos. 62-153, 308). ).

In addition, when using a some acidic addition polymerizable monomer (a), a non-acidic addition polymerizable monomer (c) should just satisfy | fill a relationship [v] with at least 1 sort (s) of acidic addition polymerizable monomer (a). .

The non-acidic addition polymerizable monomer (c) constitutes the remainder other than the acidic addition polymerizable monomer (a) and the non-acidic addition polymerizable monomer (b) in the thermoplastic polymer to be 100 parts by weight.

In addition, the styrene-based polymer is excellent in resistance to etching solution, resolution, and low temperature flow resistance. In particular, as the styrene-based polymer, 15-40% by weight of the acidic addition polymerizable monomer (a) having the carboxyl group, preferably 20-35% by weight, 1-35% by weight of the styrene-based monomer, preferably 10-35% , 84-25% by weight, preferably 70-30% by weight of acrylic and methacrylic acid esters, have excellent resistance to alkaline developers, etching solutions and plating solutions, and have excellent resolution and low temperature flow resistance. .

In light containing the alkali-soluble thermoplastic polymer which superposed | polymerized by using together a styrene-type monomer, an acrylic acid ester, and methacrylic acid ester rather than the alkali-soluble thermoplastic polymer which superposed | polymerized by combining the said styrene-type monomer and the component of acrylic ester or methacrylic acid ester. The resolution of the synthetic composition is excellent.

A combination of a styrene-based monomer with an acrylic ester having an alkyl group having 7 or more carbon atoms and a methacrylic acid ester having an alkyl group having 1 to 20 carbon atoms as a component other than an acidic addition polymerizable monomer to further increase the resolution; A combination of a styrene monomer and an acrylic acid ester having an alkyl group having 1 to 20 carbon atoms and a methacrylic acid ester having an alkyl group having 1 to 3 carbon atoms is preferable. It is preferable to use especially combining the acrylic ester which has a C7 or more alkyl group, and the methacrylic acid ester which has a C1-C3 alkyl group.

In addition, the ratio of the acrylic ester and methacrylic ester used together with the styrene monomer can be appropriately set within a range that does not reduce the resolution, acrylic ester / methacrylic ester = 20-65 / 80-35% by weight , Preferably 30-50 / 70-50% by weight.

The thermoplastic polymer is usually contained in the photopolymerizable composition at 30-80% by weight, preferably 40-70% by weight. In addition, a thermoplastic polymer can be obtained by conventional polymerization methods, such as solution polymerization, block polymerization, suspension polymerization, and emulsion polymerization. The weight average molecular weight of the thermoplastic polymer is usually about 1 x 10 ^4-1 x 10 ⁶ .

The photopolymerizable composition for coatings and resists of the present invention may contain a stabilizer, a colorant, a plasticizer, a filler, or the like which suppresses the thermal polymerization reaction and improves storage stability. As a stabilizer, p-methoxy phenol, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol etc. are illustrated, for example, and it uses suitably in the range which does not impair photopolymerization property. As the colorant, for example, dyes and pigments such as crystal violet, malachite green, Victoria blue and methylene blue are exemplified. As a plasticizer, For example, phthalic acid ester, such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate; Fatty acid esters such as dioctyl adipate and dibutyl diglycol adipate; Phosphoric acid esters such as trimethylphosphine; Sulfonic acid amides such as toluene sulfonic acid amide and the like. Examples of the filler include talc, kaolin, calcium carbonate, barium sulfate and the like.

The photosensitive layer made of the photopolymerizable composition for coating is usually formed by printing or applying a liquid photopolymerizable composition to a coating material, for example, paper, plastic or metal. As the application means, conventional means such as spray coating, dip coating, roller coating, doctor blade coating and the like are adopted.

The photopolymerizable composition for photoresist is usually used in the form of a liquid, preferably a photosensitive film, dissolved or dispersed in an organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol and propanol, alicyclic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, acetone and methyl ethyl ketone Examples thereof include ketones, diethers, tetrahydrofuran and the like, halogenated hydrocarbons such as ethers and methylene chloride, and mixed solvents thereof. The photosensitive film is usually produced by applying and drying a liquid photopolymerizable composition to a base film such as a polyethylene terephthalate film and laminating a protective film such as a polyethylene film with a pressure roll or the like. In addition, a protective film is not necessarily required. In the photosensitive film, the film thickness of the photosensitive layer made of the photopolymerizable composition is not particularly limited as long as the resolution and workability are not reduced, but is usually 50-100 μm, preferably 20-70 μm. The photosensitive film is usually wound on a roll or preserved in a laminated state.

The photopolymerizable composition for photoresist applies a liquid photopolymerizable composition containing an organic solvent to a substrate, removes the organic solvent, or peels off the protective film of the photosensitive film, and if necessary, interposes the photosensitive layer. By laminating a base film on the substrate with a rubber roll or the like.

Regardless of whether it is for coating or photoresist, the photosensitive layer is exposed to a light source that chemically generates active light, such as a low pressure mercury lamp, an ultra high pressure mercury lamp, or a xenon lamp. As the active light, a light ray having a wavelength suitable for the absorption wavelength of the photopolymerization initiator, and preferably an active light ray having a wavelength in the ultraviolet to visible region having a wavelength of 250 to 500 μm is mainly used. Moreover, an electron beam, X-rays, etc. can also be used.

In the case of the photosensitive film, exposure is normally performed by the close_contact | adhesion method or the projection method which exposes a negative or positive pattern mask film by contact | adhering to a base film.

After exposure, it develops and a resist image is formed. The development can be carried out by a suitable developing method depending on the type of thermoplastic resin as described above. Peeling phenomenon is performed by peeling a base film with the photosensitive layer of a non-exposed part. In solvent development, conventional organic solvents such as trichloroethylene and methylene chloride are usually used. In alkaline development, an alkaline developer containing a basic compound is used. Examples of the basic compound include pyrolic acid, such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium silicate, sodium phosphate, sodium pyrrolate, and potassium pyrrolate. Alkali metal salts; Butylamine, dimethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine; Organic bases, such as morpholine and pyridine, are illustrated. PH of these alkaline developing solutions is about 9-11 normally, and the sodium carbonate aqueous solution is used suitably. The developing solution may contain organic solvents such as ethylene glycol monobutyl ether, a surfactant, an antifoaming agent, and the like.

In the manufacture of a printed wiring board, the resist image is treated with a plating solution or an etching solution, and then the resist image is removed with a strong alkali aqueous solution, for example, an aqueous 2-10 wt% sodium hydroxide solution.

[Industry availability]

The photopolymerizable composition of the present invention is a coating material; glue; Printed wiring boards; It can be used for the photoresist for manufacturing a circuit board, a metal relief shape, a printing board, etc.

Next, Examples and Comparative Examples of the present invention are presented, but the present invention is not limited to these Examples.

EXAMPLE

Example 1-4 and Comparative Example 1-8

The photopolymerization initiator was mixed with the solution of the addition polymeric compound which consists of the following components in the ratio of Table 8, and the photopolymerizable composition was obtained.

15 g of trimethylolpropane triacrylate

Tetraethylene glycol acrylate 10 g

Methyl ethyl ketone 30 g

Each photopolymerizable composition was applied to each copper plate using a spatula, and then dried to form a photosensitive layer. Subsequently, at a distance of 50 cm from a 2 Kw ultra-high pressure mercury lamp in air, it irradiated until the adhesiveness of the photosensitive layer disappeared, and this irradiation period was made into hardening time. The results are shown in Table 8.

In the table, each component represents the following compound.

Component (A): 4-banjoyl-4'-methyldiphenylsulfide

Component (B): Benzophenone

Component (C): 4,4'-bis (diethylamino) benzophenone

Component (D): 2,2'-di (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole

Component (E): leuco crystal violet

Component (F): ethyl p- (diethylamino) benzoate

As is apparent from Table 8, the photopolymerizable composition of each example is cured for a short time as compared to each comparative example.

Example 5

Except having changed the component (A) into 4-benzoyl-4'-ethyldiphenyl sulfide and using it, it carried out similarly to Example 1, and investigated the hardening time, and it hardened in 8 second.

Example 6

Except for changing component (C) to 4,4'-bis (diethylamino) benzophenone and using it, the curing time was examined in the same manner as in Example 1, and cured in 8 seconds.

Example 7

Curing time in the same manner as in Example 1, except that component (D) was replaced with 2,2'-diP-methoxyphenyl-4,4,5 ', 5'-tetraphenylbisimidazole. It was found that it cured in 8 seconds.

Example 8

Except having changed the component (E) into leuco malachite green, it hardened in 8 second as a result of having investigated the hardening time similarly to Example 1.

Example 9

Except having changed the component (F) into ethyl p- (diethylamino) benzoate and using it, it investigated in hardening time similarly to Example 1, and it hardened | cured in 8 second.

[Examples 10 to 18 and Comparative Examples 9 to 12]

The following components were mixed to obtain solution A.

50 g of copolymer (acid value 130) of 20 weight% of methacrylic acid, 60 weight% of methyl methacrylate, and 20 weight% of butyl acrylate

15 g of trimethylolpropane triacrylate

10 g of 2,2'-bis (4-acryloyl diethoxyphenyl) propane

Diamond Green GH 0.03g

Methyl ethyl ketone 70 g

20 g tetrahydrofuran

This solution A was mixed with the photoinitiator in the ratio of Table 9, and the photopolymerizable composition was obtained. 25 micrometers in thickness was apply | coated to the base film which consists of polyethylene terephthalate films, and the photopolymerizable composition was dried at the temperature of 75 degreeC, and the photosensitive film was produced. The film thickness of the photosensitive layer was 50 micrometers. It laminated | stacked on the copper clad laminated board which polished this photosensitive film using the rubber roller heated at 100 degreeC. The stopper 21-stage step tablet was superimposed on a base film, and cured by irradiating for 10 seconds at a distance of 50 cm from a 2 Kw ultra-high pressure mercury lamp, and then peeling off the base film, spray-developing for 70 seconds with a 1% aqueous sodium carbonate solution at a temperature of 30 ° C, and forming a resist image. Formed. This resist image is formed corresponding to the step tablet in which the amount of transmitted light has changed in stages. Therefore, photopolymerization was judged as the number of stage tablets corresponding to the lowest exposure amount required to form a resist image. The larger the number indicating the number of steps of the step tablet, the higher the sensitivity of the photopolymerizable composition.

Subsequently, the copper clad laminate in which the resist image was formed was etched with cupric chloride etching solution and treated with a plating solution.

This result is shown in Table 9 with the composition of a photoinitiator.

In the table, each component represents the following compound.

Component (a): 4-banjoyl-4'-methyldiphenylsulfide

Component (b): Benzophenone

Component (c): 4,4'-bis (diethylamino) benzophenone

Component (d): 2,2'-di (2-chlorophenyl) -4,5,4 ', 5'-tetraphenylbisimidazole

Component (e): leuco crystal violet

Component (f): ethyl p- (diethylamino) benzoate

As is apparent from Table 9, when the photopolymerization initiator of each example is used as compared to Comparative Examples 9-12, the curing is performed in a short time. In addition, any of the resist images obtained from the photopolymerizable composition of Examples 10-13 exhibited sufficient resistance to etching liquids or plating liquids.

Example 14-20 and Comparative Example 13-15

Solution B was prepared by mixing the following ingredients.

50 g of copolymer (acid value 130) of 20 weight% of methacrylic acid, 60 weight% of methyl methacrylate, and 20 weight% of isobutyl acrylate

0.8 g of 4-banjoil-4'-methyldiphenylsulfide

0.6 g of p- (diethylamino) benzoate

Benzophenone 2.0g

0.2 g of 4,4'-bis (diethylamino) benzophenone

2,2'-di (2-chlorophenyl) -4,4,5 ', 5'-

Tetraphenylbisimidazole 1.5g

Roico Crystal Violet 0.3g

Methyl ethyl ketone 70 g

20 g tetrahydrofuran

The addition polymeric compound was mixed with this solution B in the ratio shown in Table 10, and the photopolymerizable composition was obtained. In addition, in Table 10, what was shown by the compound number shows the number of the phthalic acid derivative shown in the said Table 1-7.

And in the same manner as in Example 10, a photosensitive film was produced and the curing time of the photopolymerizable composition was measured. In addition, the minimum time required for development was measured by the same spray development as in Example 10. Alternatively, the copper clad laminate having the resist image formed thereon was etched with a cupric chloride etching solution, treated with a plating solution, and then immersed in a 2 wt% aqueous sodium hydroxide solution at a temperature of 50 ° C., and the time until the resist image was peeled off was measured. The results are shown in Table 10.

In the table, abbreviations represent the following compounds.

TMPTA: triethylolpropane triacrylate

NEGDMA: Nonnaethyl Glycol Dimethacrylate

A-BPE-4: 2,2-bis (4-acryloyldiethoxyphenyl) propane

As is apparent from Table 10, the photopolymerizable composition of Comparative Example 13-15 does not have sufficient characteristics of photopolymerization, developability and peelability on resist. On the other hand, the photopolymerizable composition of Example 14-20 was found to be photopolymerized in a short time and to be developed in a short time, and to peel off the resist image in a short time. In addition, any of the resist images of Examples 14-20 exhibited sufficient resistance to etching liquids or plating liquids.

Example 21

The following components were mixed to obtain a photopolymerizable composition.

50 g of copolymer (acid value 182) of 10% by weight of methacrylic acid, 15% by weight of acrylic acid, 52% by weight of methyl methacrylate, and 23% by weight of 2-ethylhexyl acrylate

Compound Number 6 30 g

0.8 g of 4-banjoil-4'-methyldiphenylsulfide

0.6 g of p- (diethylamino) benzoate

Benzophenone 2.0g

0.2 g of 4,4'-bis (diethylamino) benzophenone

2,2'-di (2-chlorophenyl) -4,4,5 ', 5'-

Tetraphenylbisimidazole 1.5g

Roico Crystal Violet 0.3g

Victoria Blue GH 0.1g

Methyl ethyl ketone 70 g

Tetrahydrofuran 10g

Example 22

Instead of the copolymer of Example 21, except that 50 g of copolymer (acid value 130) of 20% by weight of methacrylic acid, 45% by weight of methyl methacrylate, and 35% by weight of 2-phenoxyethyl acrylate was used. In the same manner as in 21, a photopolymerizable composition was prepared.

Example 23

Instead of the copolymer of Example 21, using 50 g of copolymer (acid value 200) of 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 40% by weight of methyl methacrylate and 32% by weight of 3-phenoxypropyl acrylic acid was used. Except for the same as in Example 21 to prepare a photopolymerizable composition.

Example 24

Instead of the copolymer of Example 21, 50 g of copolymer (acid value 200) of 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 30% by weight of styrene, 17.5% by weight of 2-ethylhexyl acrylate and 24.5% by weight of methyl methacrylate Except for using the same as in Example 21 to prepare a photopolymerizable composition.

Example 25

Instead of the copolymer of Example 21, a copolymer of 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 10% by weight of styrene, 22% by weight of 2-ethylhexyl acrylate and 40% by weight of methyl methacrylate (acid value 200) was added. Except for using it, it carried out similarly to Example 21, and prepared the photopolymerizable composition.

Example 26

Instead of the copolymer of Example 21, a copolymer of 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 25% by weight of styrene, 17% by weight of 2-ethylhexyl acrylate and 30% by weight of methyl methacrylate (acid value 200) was added. Except for using it, it carried out similarly to Example 21, and prepared the photopolymerizable composition.

Example 27

Instead of the copolymer of Example 21, except using a copolymer of 20% by weight of methacrylic acid, 30% by weight of styrene, 24% by weight of 2-ethylhexyl acrylate, 26% by weight of methyl methacrylate (acid value 130) In the same manner as in Example 21, a photopolymerizable composition was prepared.

Example 28

Instead of 30 g of the addition polymerizable compound (Compound No. 6) of the photopolymerizable composition of Example 21, Compound No. 22.4 g, Trimethylolpropane triacrylate 11 g, 2,2'-bis (4-acryloyl diethoxyphenyl) A photopolymerizable composition was prepared in the same manner as in Example 21 except that 4 g of propane and 3 g of nonaethylene glycol dimethacrylate were used.

[Comparative Example 16]

Instead of the copolymer of Example 21, 6% by weight of methacrylic acid, 6% by weight acrylic acid, 30% by weight styrene, 17.5% by weight 2-ethylhexyl acrylate, 40.5% by weight methyl methacrylate (acid value 85.5) were added. Except for using it, it carried out similarly to Example 21, and prepared the photopolymerizable composition.

Then, in the same manner as in Example 10, a photosensitive film was prepared to evaluate the sensitivity of the photopolymerizable composition and the peeling time of the resist phase, and at the same time, the resolution, resistance to alkali liquid, and low temperature flow resistance were evaluated as follows. It was.

(1) Resolution Evaluation Method

As a pattern mask, spray developing and washing with water in the same manner as in Example 10 using five pairs of silver salt pattern masks each having a line width and a space of 10 µm to 150 µm in a 1: 1 area ratio on a 10 µm cutout. did. And the resist image is observed with the optical microscope of 200x magnification, and the minimum mask line width without the meandering of a line and the bridge | bridging of a resist in a space part is shown as the resolution.

(2) Evaluation method of resistance to alkali liquid

In addition, the resist film was formed under the same conditions as in Example 10 without using the pattern mask. This resist film was immersed in 1 weight% sodium carbonate aqueous solution adjusted to pH 8.5 for 1 hour, and the resistance to alkaline liquid was visually judged. Resistance to alkaline liquids was evaluated based on the following criteria.

Right: no change in resist film

Amount: Swell slightly of resist film

(3) Evaluation method of low temperature flow resistance

On the photosensitive layer of the photosensitive film, the polyethylene film of 20 micrometers in thickness was laminated, and while winding up while applying a tension, the dry film of the wound state was produced. The dry film of the wound state was raised and stored at room temperature, and the period until the photopolymerizable composition leaked from the dry film edge part was investigated on the following reference | standard, and it was set as the index of low temperature flow resistance.

Right: 6 months or more

Quantity: 1-4 months

The obtained results are shown in Table 11.

As shown in Table 11, compared with the photopolymerizable composition of Comparative Example 16, the photopolymerizable composition of Examples 21-28 was excellent in photopolymerization, resist peeling property, resolution, and resistance to alkali liquid, and low temperature flow resistance was also good. Do. In addition, any of the resist images of Examples 21-28 exhibited sufficient resistance to etching liquid or plating liquid.

Remarks: In the photopolymerizable composition of Comparative Example 16, after development, a resist-like residual film adhered, and accurate photopolymerization, resolution, and resistance to alkali liquid could not be evaluated.

Claims (40)

A photopolymerizable composition containing at least a photopolymerization initiator and an addition polymerizable compound in a liquid or a solid at ordinary temperature and pressure, wherein the photopolymerization initiator contains at least the following components (A) to (E). (A) sulfide compounds represented by the general formula [I] (In formula, R <^1> , R <^2> and R <^3> is the same or different from each other, and is a group selected from the group which consists of a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group, and an aralkyl group. 1 and n are integers of 1-5, m represents an integer of 1-4). (B) The benzophenone type compound which may have a substituent selected from the group which consists of an aryl group, an alkoxycarbonyl group, and an alkoxy group which may have a halogen atom, an alkyl group, and a substituent. (C) Alkylamino benzophenone type compound which may have a substituent selected from the group which consists of a halogen atom, an alkyl group, and an aryl group which may have a substituent, an alkoxycarbonyl group, and an alkoxy group. (D) 2,4,5-triaryl imidazolyl dimer which may have a substituent, and (E) triaryl methane leuco dye. The sulfide compound represented by the general formula [I], wherein R ¹ and R ³ are hydrogen atoms, and R ³ is an alkyl group having 1 to 6 carbon atoms. The sulfide compound represented by the general formula [I] is 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'ethyldiphenylsulfide, 4-benzoyl-4 ' A photopolymerizable composition which is -propyldiphenyl sulfide, 4-benzoyl-4'-isopropyldiphenyl sulfide, 4-benzoyl-4'-butyldiphenyl sulfide. The photopolymerizable composition according to claim 1, wherein the benzophenone compound is benzophenone. The photopolymerizable composition according to claim 1, wherein the alkylaminobenzophenone-based compound is 4, 4'-bis (dialkyl amino) benzophenone. The compound according to claim 1, wherein the alkylaminobenzophenone compound is 4, 4'-bis (dimethylamino) benzophenone, 4-dimethylamino-4'-diethylaminobenzophenone, 4, 4'-bis (diethylamino ) Benzophenone, 4, 4'-bis (dipropylamino) benzophenone, 4, 4'-bis (diisopropylamino) benzophenone, 4, 4'-bis (dibutylamino) benzophenone, 4, 4 A photopolymerizable composition which is' -bis (diisobutylamino) benzophenone or 4, 4'-bis (di-t-butylamino) benzophenone. The photopolymerizable composition according to claim 1, wherein the 2,4,5-triaryl imidazolyl dimer which may have a substituent is a compound represented by the following general formula [II]. In formula, Ar <^1> , Ar <^2> and Ar <^3> represent the aryl group which may have a substituent. The 2,4,5-triaryl imidazolyl dimer according to claim 1, which may have a substituent, is 2,2 ', 4,4', 5,5'-hexaphenylbisimidazole, 2,2'- Di (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (p-chlorophenyl) -4,4', 5,5'-tetraphenylbis Imidazole, 2,2'-di (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) bisimidazole, 2,2'-di (p-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) bisimidazole, 2,2'-di (o-fluorophenyl) -4,4', 5,5'-tetraphenylbis Imidazole, 2,2'-di (p-fluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-di (p-methoxyphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-di ( 2,4-dimethoxyphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2', 4,4'-tetra (p-methoxyphenyl) -5,5'-di Phenylbisimidazole, 2,2'-di (p-methylthiophenyl) -4,4 ', 5,5'-tetraphenyl ratio A photopolymerizable composition which is sumidazole. The method of claim 1, wherein the triarylmethaneco dye is selected from tris (4-N, N-diethylamino-o-tolyl) methane, bis (4-N, N-diethylamino-o-tolyl) thienyl methane, Bis (4-N, N-diethylamino-o-tolyl) benzylthiophenylmethane, leuco malachite green (C. I. Basic green 4), cocoic crystal violet (C. I. Basic violet 3), brilliant green (C. I. Basic green 1), Victoria Green 3B (C. I. Basic green 4), Acid Green GG (C. I. Basic green 1), Methyl violet (C. I. Basic violet 1), Rose Photopolymerizable composition which is aniline (C. I. Basic violet 14) or salts thereof. The polymer initiator is 50-500 parts by weight of the benzophenone compound, 5-250 parts by weight of the alkylaminobenzophenone compound, 2,4, based on 100 parts by weight of the compound represented by the general formula [I]. 50-400 parts by weight of 5-triarylimidazolyl dimer and 10-70 parts by weight of triarylmethaneroic dye. The photopolymerizable composition according to claim 1, which contains a p-(dialkylamino) benzoic acid alkyl ester. The photopolymerizable composition according to claim 11, wherein the p-(dialkylamino) benzoic acid alkyl ester is a compound represented by the following general formula [III]. In the formula, R ⁴ , R ⁵ and R ⁶ are the same as or different from each other and represent a lower alkyl group. The p- (dialkylamino) benzoic acid alkyl ester of claim 11 wherein the p- (dialkylamino) benzoic acid alkylester is p- (dimethylamino) benzoic acid methyl, p- (dimethylamino) benzoic acid ethyl, p- (dimethylamino) benzoic acid propyl, p- (dimethylamino) Isopropyl benzoate, methyl p- (N-methyl-N-ethylamino) benzoate, ethyl p- (N-methyl-N-ethylamino) benzoate, methyl methyl p- (diethylamino), p-(diethylamino Ethyl benzoate, p- (diethylamino) benzoic acid propyl, p- (diethylamino) benzoic acid isopropyl, p- (dipropylamino) benzoic acid methyl, p- (dipropylamino) benzoic acid ethyl, p- (dipropyl Amino) benzoic acid propyl, p- (dipropylamino) benzoic acid isopropyl. The photopolymerizable composition of Claim 11 which consists of 25-200 weight part of p- (dialkylamino) benzoic acid alkyl esters with respect to 100 weight part of sulfide type compounds represented by general formula [I]. The photopolymerizable composition according to claim 1, wherein the addition polymerizable compound has two or more acryloyl groups or methacryloyl groups in the molecule. The photopolymerizable composition according to claim 1, wherein 0.1-30 parts by weight of the photopolymerization initiator is incorporated with respect to 100 parts by weight of the addition polymerizable compound. The photopolymerizable composition according to claim 1, which contains a photopolymerization initiator, an addition polymerizable compound of a liquid or a solid, and a thermoplastic polymer at room temperature and normal pressure. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains at least the compound represented by the following general formula [IV]. Wherein R ⁷ and R ¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ⁸ , R ⁹ are the same or different and represent a straight or branched alkylene group, R ¹¹ is a hydrogen atom, a halogen atom or An alkyl group having 1 to 10 carbon atoms is represented, p and q are each an integer of 1-10, and r represents an integer of 1-20. The photopolymerizable composition according to claim 18, wherein the compound represented by the general formula [IV] is a phthalic acid derivative. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains 5% by weight or more of the compound represented by the general formula [IV]. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains a compound represented by the general formula [IV] and a (meth) acrylate having three (meth) acryloyl groups in the molecule. 22. The photopolymerizable composition according to claim 21, wherein the (meth) acrylate having three (meth) acryloyl groups in the molecule is trimethylolpropane tri (meth) acrylate. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains a compound represented by the general formula [IV] and a compound represented by the following general formula [IV]. In the formula, R ¹² , R ¹³ and R ¹⁴ are the same as or different from each other, represent a hydrogen atom or a methyl group, and s represents an integer of 7-11. The photopolymerizable composition according to claim 23, wherein in the compound represented by the general formula [V], R ¹³ is a hydrogen atom, R ¹² and R ¹⁴ are a hydrogen atom or a methyl group, and s is 8-10. The photopolymerizable composition according to claim 17, wherein the addition polymerizable compound contains a compound represented by the general formula [IV] and a compound represented by the following general formula [IV]. In formula, R <^15> , R <^16> , R <^17> and R <^18> are the same or different from each other, represent a hydrogen atom or a methyl group, t and u represent the integer of 1-15. The photopolymerizable according to claim 25, wherein in the compound represented by the general formula [VI], R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each hydrogen atoms, t is 1-5 and u is 1-5. Composition. 18. The compound represented by the general formula [IV] and the compound represented by the general formula [IV] and (meth) acrylate having three (meth) acryloyl groups and the general formula [V] The photopolymerizable composition containing the compound represented by Formula [IV]. 28 to 40 parts by weight of the compound represented by the general formula [IV], with respect to 100 parts by weight of the thermoplastic polymer, 10 to 40 parts by weight of (meth) acrylate having three (meth) acryloyl groups in the molecule. A photopolymerizable composition containing 2-15 parts by weight of a compound represented by formula [V] and 5-20 parts by weight of a compound represented by formula [IV]. The photopolymerizable composition of claim 17 wherein the thermoplastic polymer is an alkali soluble polymer. 18. The photopolymerizable composition of claim 17, wherein the thermoplastic polymer has an acid value of 100-350. The photopolymerizable composition according to claim 17, wherein the thermoplastic polymer is a copolymer of 15-40 wt% of the acidic addition polymerizable monomer having a carboxyl group and 85-60 wt% of the non-acidic addition polymerizable monomer. 32. The photopolymerizable composition of claim 31 wherein the acidic addition polymerizable monomer having a carboxyl group is methacrylic acid, acrylic acid or a mixture thereof. The photopolymerizable composition according to claim 31, wherein the non-acidic addition polymerizable monomer is at least one of styrene, α-methylstyrene, and (meth) acrylic acid esters having 1 to 20 carbon atoms. 18. The photopolymerizable composition of claim 17 wherein the thermoplastic polymer is a copolymer of the following components (a)-(c). (a) 15-40% by weight of the acidic addition polymerizable monomer having a carboxyl group (b) at least 5% by weight of the non-acidic addition synthetic monomer represented by the following general formula [VII] Wherein R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ is an alkylene group having 1 to 6 carbon atoms, R ²¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and v is a positive integer of 1-20 And (c) the balance of the non-acidic addition-polymerizable monomer which has Q value and e value which satisfy | fill a relation [k]. 0.25 (QA / Qc) Exp [-eA (eA-eC)] 4.00 [Ⅷ] (wherein Q and e are the stability and polarity of the monomer defined by the formula of Alfrey-Price, Symbol A represents an acidic addition polymerizable monomer (a), symbol C represents a non acidic addition polymerizable monomer (c)) 18. The photopolymerizable composition according to claim 17, wherein the thermoplastic polymer is a copolymer of 15-40% by weight of the acidic addition polymerizable monomer having a carboxyl group, 1-35% by weight of the styrene monomer, 84-25% by weight of the acrylic acid ester and the methacrylic acid ester. . The photopolymerizable composition according to claim 35, wherein the acrylic ester is an acrylic ester having an alkyl group having 7 or more carbon atoms, and the methacrylic ester is a methacrylic ester having an alkyl group having 1-20 carbon atoms. The photopolymerizable composition according to claim 35, wherein the acrylic ester is an acrylic ester having an alkyl group having 1 to 20 carbon atoms, and the methacrylic ester is a methacrylic ester having an alkyl group having 1 to 3 carbon atoms. The photopolymerizable composition according to claim 35, wherein the acrylic acid ester is an acrylic acid ester having an alkyl group having 7 or more carbon atoms, and the methacrylic acid ester is a methacrylic acid ester having an alkyl group having 1 to 3 carbon atoms. 36. The photopolymerizable composition of claim 35 wherein the ratio of acrylic ester to methacrylic ester is acrylic ester / methacrylic ester = 20-65 / 80-35 wt%. The photopolymerizable composition according to claim 17, which contains 25 to 80 parts by weight of the addition polymerizable compound and 0.1-30 parts by weight of the photopolymerization initiator with respect to 100 parts by weight of the thermoplastic polymer.