JP2801047B2 - Photopolymerizable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photopolymerizable composition useful as a photoresist.

[Prior Art and Problems to be Solved by the Invention] Photopolymerizable compositions are widely used as printed wiring boards, printing plates and photoresists for forming metal relief images. The photopolymerizable composition usually contains an addition polymerizable compound having an α, β-ethylenically unsaturated bond, a photopolymerization initiator, and a thermoplastic polymer. This photopolymerizable composition can be used in the form of a liquid, but from the viewpoint of workability and environmental pollution, a light-transmitting substrate film and a protective film are formed on both surfaces of the photosensitive layer composed of the photopolymerizable composition. And is widely used in the form of a photosensitive film in which is laminated. When producing a printed wiring board, this photosensitive film is obtained by peeling a protective film, usually laminating a base film via a photosensitive layer on a substrate such as a copper-clad laminate, and activating it through a predetermined pattern mask or the like. The exposed part is cured by exposing to light. Therefore, the photopolymerizable composition is required to have excellent photopolymerizability. Although the photopolymerizability mainly depends on the type of the photopolymerization initiator, the photopolymerization rate of the conventional photopolymerization initiator is not sufficient. That is, conventionally, as a photopolymerization initiator, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzyl, etc., a photopolymerization initiator in which benzophenone is combined with N, N'-bis (diethylamino) benzophenone, a photopolymerization initiator composed of a rofin dimer or a rofin dimer and a leukotriphenylmethane dye ( JP-B-45-37377) and the like, but a photopolymerizable composition containing these photopolymerization initiators is
The photopolymerization rate is not yet sufficient.

Also, when the thermoplastic polymer in the photopolymerizable composition is a solvent-soluble polymer or an alkali-soluble polymer, after curing the exposed portion, utilizing the difference in solubility between the exposed portion and the exposed portion, The unexposed portions are dissolved and removed with a developing solution composed of an organic solvent or an aqueous alkali solution and developed to form a resist image. When the thermoplastic polymer is chlorinated polyethylene or the like, a resist image is formed by peeling development in which the base film is peeled and developed by utilizing a difference in adhesiveness between an exposed portion and an unexposed portion of the substrate and the base film. Is formed. Therefore,
The photopolymerizable composition is required to have excellent developability and resolution. Further, when developing with a developer, it is also required to have excellent resistance to the developer. As the developer, an organic solvent-type developer such as 1,1,1-trichloroethane is known, but this developer involves problems such as contamination of the working environment and surrounding environment and an increase in manufacturing cost. Therefore, in recent years, developers comprising an aqueous alkali solution containing a basic compound such as sodium carbonate have been widely used.

After forming a resist image by the above-described development, when manufacturing a printed circuit board, an etching process or a plating process is performed using the resist image as a mask, a pattern corresponding to the resist image is formed, and the resist image is stripped with a stripping liquid. Has been removed. Therefore, the resist image is required not only to have excellent adhesion to the substrate and to have excellent resistance to an etching solution and a plating solution, but also to be quickly peeled off by a peeling solution. These characteristics greatly depend on the composition of the photopolymerizable composition, and a resist image exhibiting excellent resistance to an etching solution and a plating solution generally has high resistance to a stripping solution and poor stripping properties. In particular, since the alkali-developable photopolymerizable composition contains a thermoplastic polymer having an active carboxyl group, when the resist image is peeled with a strong alkali aqueous solution such as sodium hydroxide or potassium hydroxide, It takes a long time to peel. Therefore, not only does the productivity of the printed wiring board and the like decrease, but also the so-called "alkali burn" in which the metal substrate, particularly the copper foil of the copper-clad laminate is darkened by the alkaline aqueous solution, adversely affecting the subsequent steps.

In addition, the photosensitive film is required to have cold flow resistance, that is, not to leak the photopolymerizable composition from the end of the photosensitive film stored in a wound state.

U.S. Pat. No. 3,930,865 discloses a thermoplastic polymer comprising a polymerizable monomer having a carboxyl group, a methacrylate having an alkyl group having 4 or more carbon atoms, and 1 to 35% by weight of a styrene-based monomer. Photopolymerizable compositions containing molecules are disclosed. Also, Japanese Patent Laid-Open No. 58-12
No. 577 discloses that a polymerizable monomer having a carboxyl group is 10 to 40% by weight, a methacrylate having an alkyl group having 6 to 12 carbon atoms is 35 to 83% by weight, and a styrene monomer is 3 to 25% by weight. A photopolymerizable composition containing the constituted thermoplastic polymer is disclosed. These photopolymerizable compositions are excellent in alkali developing solution resistance and etching solution resistance, possibly due to the combination of a styrene-based monomer with methacrylic acid ester as a component of the thermoplastic polymer, and have a certain degree of cold resistance. Despite showing flow properties, the resolution is not yet sufficient.

Japanese Patent Publication No. 54-25957 discloses 15 to 40% by weight of a polymerizable monomer having a carboxyl group, 15 to 45% by weight of a methacrylate and an acrylate having an alkyl group having 1 to 6 carbon atoms, and styrene. System monomer 40-60
A photopolymerizable composition containing a polymer constituted by weight percent is disclosed. Although the photopolymerizable composition is more excellent in cold flow resistance than the thermoplastic polymer, the resolution is still insufficient as described above.

As described above, each component constituting the photopolymerizable composition has a large effect on photopolymerizability, developability, resolution, resistance of the resist film, peelability, and the like. Characteristics are not yet sufficient.

Accordingly, a main object of the present invention is to provide a photopolymerizable composition having excellent photopolymerizability.

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

It is still another object of the present invention to provide a photopolymerizable composition which can be alkali-developed and has excellent alkali developing solution resistance, etching solution resistance and plating solution resistance.

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

[Constitution of the Invention] The present invention provides a photopolymerizable composition containing a photopolymerization initiator, a thermoplastic polymer, and a liquid or solid addition polymerizable substance at normal temperature and normal pressure, wherein the photopolymerization initiator is (A) Sulfide compound represented by the following general formula [I] (Wherein R ¹ , R ² and R ³ are the same or different,
A group selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, an alkoxy group, and an aralkyl group;
Represents an integer of 1 to 5, and m represents an integer of 1 to 4. (B) a benzophenone-based compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group; c) an alkylaminobenzophenone-based compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group; A) a photopolymerizable composition comprising at least a 2,4,5-triarylimidazolyl duplex which may have a substituent, and (e) a triarylmethane leuco dye.

In the present invention, the addition-polymerizable substance may be 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 and R ⁹ are the same or different and represent a linear or branched alkylene group, R ¹¹ is a hydrogen atom, a halogen Represents an atom or an alkyl group having 1 to 10 carbon atoms, p and q each represent an integer of 1 to 10, and r represents an integer of 1 to 20). .

The present invention also provides a photopolymerizable composition in which the thermoplastic polymer contains an alkali-soluble polymer, particularly a thermoplastic polymer having an acid value of 100 to 350.

Furthermore, the present invention provides a thermoplastic polymer comprising: (A) an acid addition polymerizable monomer having a carbosyl group,
40% by weight, (B) the following general formula [VII] (In the formula, R ¹⁹ is a hydrogen atom or a methyl group, and R ²⁰ has 1 to 1 carbon atoms.
An alkylene group of 6, 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 to 20). Weight%, and (C) relational formula [VIII] 0.25 <(QA / Qc) Exp [−eA (eA−eC)] <4.00 [VII
I] (where Q and e are Alfrey-Pr
The symbol A represents the addition-polymerizable monomer (A), and the symbol C represents the non-acidic addition-polymerizable monomer (C). The present invention provides a photopolymerizable composition which is a copolymer of a non-acidic addition-polymerizable monomer having a Q value and an e value that satisfy the above conditions.

In the present invention, the thermoplastic polymer is an acid addition polymerizable monomer having a carboxyl group of 15 to 40% by weight, a styrene monomer of 1 to 35% by weight, an acrylic acid ester and a methacrylic acid ester of 84 to 25% by weight. A photopolymerizable composition which is a copolymer of

The photopolymerization initiator includes a sulfide compound represented by the general formula [I] as the component (a). General formula [I]
In the sulfide compound represented by the formula, substituents R ¹ and R ²
And examples of the alkyl group for R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and octyl groups.

Examples of the aryl group include a phenyl, naphthyl, anthryl group and the like.

As the substituent of the alkyl group, fluorine, chlorine, halogen atoms such as bromine, hydroxy group, methoxy, ethoxy,
Alkoxy groups such as propoxy group, alkoxyl group, methoxycarbonyl, ethoxycarbonyl, alkoxycarbonyl group such as propoxycarbonyl group, amino group, dimethylamino, alkylamino group such as diethylamino group,
Examples thereof include a nitro group and a cyano group. Examples of the substituent of the aryl group include the above-mentioned alkyl group and the substituent of the above-mentioned alkyl group.

Alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert
-Butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

As the aralkyl group, benzyl, phenethyl, 3-
Examples include phenylpropyl and benzhydryl groups.

The substituents R ¹ , R ² and R ³ may be substituted at an appropriate position on the benzene ring, and the same benzene ring may be substituted with the same or different substituents.

Preferred groups for 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 an alkyl group having 1 to 4 carbon atoms.

Particularly preferred compounds of the sulfide compound represented by the general formula [I] include, for example, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 4-benzoyl-4 '
-Ethyldiphenyl sulfide, 4-benzoyl-4 '
-Propyldiphenyl sulfide, 4-benzoyl-
Examples thereof include 4'-isopropyldiphenyl sulfide, 4-benzoyl-4'-butyldiphenyl sulfide, and the like.

One or more of these sulfide compounds can be used.

Further, the photopolymerization initiator contains at least one benzophenone-based compound which may have a substituent as the component (b). Examples of the substituent include the above-described halogen atoms, alkyl groups, aryl groups which may have a substituent, alkoxy groups, and alkoxycarbonyl groups. A preferred benzophenone-based compound is benzophenone. At least one of these benzophenone compounds is used.

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

Examples of the substituent of the alkylaminobenzophenone-based compound contained as the component (c) in the photopolymerization initiator include a halogen atom, an alkyl group, an aryl group which may have a substituent, an alkoxy group, and an alkoxycarbonyl group. Is exemplified. Examples of the alkylaminobenzophenone-based compound include 4-methyl-4'-diethylaminobenzophenone, 4-methoxy-4'-diethylaminobenzophenone, 4,4'-bis (methylamino) benzophenone, and 4-methylamino-4'- Ethylaminobenzophenone, 4-diethylaminobenzophenone and the like are also included. A preferred alkylaminobenzophenone-based compound is 4,4'-bis (alkylamino) benzophenone. As 4,4'-bis (alkylamino) benzophenone, for example, 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 4,4'-bis (dibutylamino) benzophenone, 4,4'-bis (diisobutylamino) benzophenone, 4,4'-bis (ditert-butylamino) benzophenone and the like. Among these compounds, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are particularly preferred.

At least one alkylaminobenzophenone compound is used.

The ratio of the alkylaminobenzophenone-based compound to 100 parts by weight of the compound represented by the general formula [I] is usually
The amount is 5 to 250 parts by weight, preferably 10 to 200 parts by weight, and more preferably 20 to 175 parts by weight. When the amount of the alkylaminobenzophenone-based compound is out of the above range, the photosensitivity decreases.

Further, the photopolymerization initiator contains, as the component (d), a 2,4,5-triarylimidazolyl duplex which may have a substituent. This 2,4,5-triarylimidazolyl duplex is represented by the following general formula [II].

(Wherein, Ar ¹ , Ar ² and Ar ³ each represent an aryl group which may have a substituent) Examples of the substituent include a halogen atom and an alkoxy group exemplified above, and alkylthio such as methylthio and ethylthio groups. Groups are exemplified.

As the 2,4,5-triarylimidazolyl dimer represented by the general formula [II], for example, 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'-tetraphenylbisimidazole, 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'-tetraphenylbisimidazole, 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'-
Examples thereof include diphenylbisimidazole and 2,2'-di (p-methylthiophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole. At least one 2,4,5-triarylimidazolyl dimer represented by the above general formula [II] is used.

The 2,4,5-triarylimidazolyl dimer is generally used in an amount of 50 parts by weight based on 100 parts by weight of the compound represented by the general formula [I].
400400 parts by weight, preferably 100-300 parts by weight. When the amount of the 2,4,5-triarylimidazolyl duplex is out of the above range, the photosensitization is not sufficient.

Further, the photopolymerization initiator contains a triarylmethane leuco dye as the component (e). The triarylmethane leuco dye preferably has at least one dialkylamino group in the substituted amino group, and functions as a free radical generator. As the triarylmethane leuco dye, for example, tris (4-N, N
-Diethylamino-o-tolyl) methane trihydrochloride, bis (4-N, N-diethylamino-o-tolyl) thienylmethane, bis (4-N, N-diethylamino-o-tolyl) benzylthiophenylmethane, leucomalachite green (CIBasic green 4), leuco crystal violet (CIBasic violet 3), brilliant green (CIBasic green 1), Victoria green 3B (C.
I.Basic green 4), Acid Green GG (CIAcid gr
een 3), methyl violet (CIBasic violet)
1), Roseaniline (CIBasic violet 14) and the like. These triarylmethane leuco dyes can be used as mineral salts such as hydrochloride and sulfate, and organic acid salts such as p-toluenesulfonate. At least one triarylmethane leuco dye can be used.

Triarylmethane leuco dye is usually 10 to 70 parts by weight, based on 100 parts by weight of the compound represented by the general formula [I],
It is preferably used in a proportion of 25 to 55 parts by weight. When the amount of the triarylmethane leuco dye is out of the above range, the photosensitivity decreases.

(A) a sulfide compound represented by the general formula [I],
Contains a photopolymerization initiator consisting of a combination of (b) a benzophenone compound, (c) an alkylaminobenzophenone compound, (d) a 2,4,5-triarylimidazolyl duplex, and (e) a triarylmethane leuco dye. In order to further enhance the photopolymerizability of the photopolymerizable composition, the photopolymerization initiator preferably contains (f) alkyl p- (dialkylamino) benzoate.

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

(Wherein R ⁴ , R ⁵ and R ⁶ are the same or different and represent a lower alkyl group) Examples of the lower alkyl group include methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, tert-
Examples thereof include linear or branched alkyl groups such as butyl, pentyl, hexyl, and octyl groups. Among these alkyl groups, an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 3 carbon atoms is preferable.

Preferred alkyl p- (dialkylamino) benzoates include, for example, methyl p- (dimethylamino) benzoate, ethyl p- (dimethylamino) benzoate, propyl p- (dimethylamino) benzoate and p- (dimethylamino) benzoate.
Isopropyl (dimethylamino) benzoate, p- (N-
Methyl-N-ethylamino) methyl benzoate, p- (N
-Methyl-N-ethylamino) ethyl benzoate, p-
Methyl (diethylami) benzoate, ethyl p- (diethylamino) benzoate, propyl p- (diethylamino) benzoate, isopropyl p- (diethylamino) benzoate, methyl p- (dipropylamino) benzoate, p-
Examples thereof include ethyl (dipropylamino) benzoate, propyl p- (dipropylamino) benzoate, and isopropyl p- (dipropylamino) benzoate. General formula [II
The p- (dialkylamino) benzoic acid alkyl ester represented by I] can be used alone or in combination of two or more.

The alkyl p- (dialkylamino) benzoate is a sulfide compound represented by the above general formula [I].
With respect to 0 parts by weight, usually 25 to 200 parts by weight, preferably 50
Used in a proportion of ~ 100 parts by weight. When the amount of the alkyl p- (dialkylamino) benzoate is out of the above range, the polymerization rate of the photopolymerizable composition tends to decrease.

The reason that the photopolymerization initiator composed of the components (a) to (e) or the components (a) to (f) exhibits a high photopolymerization rate is that excitation of the photopolymerization initiator by light irradiation and energy transition proceed smoothly. However, it is presumed that the addition-polymerizable substance is efficiently subjected to radical polymerization.

The photopolymerization initiator contains, as necessary, substituted or unsubstituted polynuclear quinones, benzoins, benzoin ethers, substituted or unsubstituted thioxanthones, and other photopolymerization initiators. Is also good. Examples of the substituted or unsubstituted polynuclear quinones include, for example, 2-methylanthraquinone, 2-ethylanthraquinone, 2-propylpyranthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-dimethylanthraquinone, and 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-
Tetrahydronaphthacenequinone and the like are exemplified. Examples of benzoins and benzoin ethers include benzoin, methyl benzoin, ethyl benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin fenyl ether, and the like. Examples of substituted or unsubstituted thioxanthones include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Examples thereof include dibutylthioxanthone. Examples of other photopolymerization initiators include oxime esters such as benzyl, α, α-diethoxyacetophenone, and benzophenone oxime acetate.

The amount of the photopolymerization initiator to be used is generally 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the thermoplastic polymer. When the amount of the photopolymerization initiator is less than 0.1 part by weight, the photopolymerizability decreases, and when it exceeds 30 parts by weight, the stability of the photopolymerizable composition decreases.

It is useful to use the photopolymerization initiator in combination with an appropriate amount of an aliphatic or aromatic amine. Examples of the aliphatic or aromatic amines include 2-mercaptobenzoxazole, ethanolamine, diethanolamine, triethanolamine, diethylaminoethanol, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine,
Allylthiourea, N, N-diethylglycine, aniline,
N-methylaniline, N, N-diethylaniline, N-ethylmorpholine and the like are exemplified.

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

In order to remove the resist film in a short time, the addition-polymerizable substance preferably contains at least the component (1): a 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 and R ⁹ are the same or different and represent a linear or branched alkylene group, R ¹¹ is a hydrogen atom, a halogen Represents an atom or an alkyl group having 1 to 10 carbon atoms, p and q each represent an integer of 1 to 10, and r represents an integer of 1 to 20) In the general formula [IV], as the alkylene group of R ⁸ and R ⁹ Is exemplified by methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group, heptamethylene, octamethylene group and the like. Examples of the halogen atom and alkyl group for R ¹¹ include the same halogen atom and alkyl group as described above.

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

In the compound represented by the general formula [IV], the carbonyl group substituted on the benzene ring has the other carbonyl group at the o-, m-, and p-positions with respect to one carbonyl group. That is, a phthalic acid derivative, an isophthalic acid derivative, and a terephthalic acid derivative. Preferred examples of the compound represented by the general formula [IV] include phthalic acid derivatives shown in the following table.

The compound represented by the general formula [IV] as the component (1) can be used alone or as a mixture of two or more.

The compound represented by the general formula [IV] is contained in the addition-polymerizable substance at least 5% by weight or more, preferably 10 to 75% by weight, more preferably 15 to 50% by weight. If the amount of the compound represented by the general formula [IV] is less than 5% by weight, it takes a long time for the resist film to be stripped by the stripping solution depending on the type of the thermoplastic polymer.

The addition-polymerizable substance includes, in addition to the above compound (1), that is, the compound represented by the general formula [IV], the following components (2) to
Any one of the components (4), in particular, the components (2) to
It is preferable to use (4) in combination. The photopolymerizable composition containing the addition polymerizable substance composed of such a combination can remove the resist film in a short time, and has photopolymerizability, developability, developer resistance, etching resistance and plating resistance. It satisfies various required characteristics such as properties in a well-balanced manner.

Component (2): (Meth) acrylate having three (meth) acryloyl groups in the molecule Examples of the (meth) acrylate having three (meth) acryloyl groups in the molecule as the component (2) include: Glycerin triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, and methacrylates corresponding thereto. Of these (meth) acrylates, trimethylolpropane tri (meth) acrylate is preferred. Component (2) can be used as one kind or as a mixture of two or more kinds.

Component (3): a compound represented by the following general formula [V] (Wherein, R ¹² , R ¹³ and R ¹⁴ are the same or different and each represent a hydrogen atom or a methyl group, and s represents an integer of 7 to 11.) In the above general formula [V] as the component (3), The compounds represented include, for example, heptaethylene glycol diacrylate, octaethylene glycol diacrylate, nonaethylene glycol diacrylate, decaethylene glycol diacrylate, undecaethylene glycol diacrylate, heptapropylene glycol diacrylate, octapropylene glycol Examples include diacrylate, nonapropylene glycol diacrylate, decapropylene glycol diacrylate, undecapropylene glycol diacrylate, and dimethacrylate corresponding thereto. Among these compounds, R ¹³ is a hydrogen atom, R ¹² and R ¹⁴ are each a hydrogen atom or a methyl group, diacrylates or dimethacrylates of repeating units s = 8 to 10 are preferred. Component (3) can be used as one kind or as a mixture of two or more kinds.

Component (4): a compound represented by the following general formula [VI] (Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different,
A hydrogen atom or a methyl group, and t and u each represent an integer of 1 to 15) The compound represented by the above general formula [VI] as the component (4) includes, for example, 2,2-bis (4- Acryloylethoxyphenyl) propane, 2,2-bis (4-acryloyldiethoxyphenyl) propane, 2,2-bis (2-acryloyltriethoxyphenyl) propane, 2,2-bis (4-acryloyltetraethoxyphenyl) 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-acryloylidedecaethoxyphenyl) propane, 2,2-bis (4-acryloylpentadecaethoxyphenyl) propane, 2,2-bis (4-acryloylpropoxyphenyl) propane, 2,2-bis (4-acryloyldipropoxyphenyl) propane,
2,2-bis (4-acryloyltripropoxyphenyl) propane, 2,2-bis (4-acryloyltetrapropoxyphenyl) propane, 2,2-bis (4-acryloylpentapropoxyphenyl) propane, 2,2-bis (4-acryloylhexapropoxyphenyl) propane, 2,2-bis (4-acryloyloctapropoxyphenyl) propane, 2,2-bis (4-acryloyldecapropoxyphenyl) propane, 2,2-bis (4-acryloylidedeca) Propoxyphenyl) propane, 2,2
-Bis (4-acryloylpentadecapropoxyphenyl) propane and methacrylate corresponding thereto.

Among the components (4) represented by the general formula [VI], preferred compounds are those in which R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are all hydrogen atoms, a repeating unit t = 1 to 5, a repeating unit u = 1 ~
5, especially t = 2-4, u = 2-4. Component (4) can be used as one kind or as a mixture of two or more kinds.

The ratio of each of the above components (1) to (4) with respect to the thermoplastic polymer can be determined within a range that does not impair photopolymerizability, developability, developer resistance, and the like. The proportions of the components (1) to (4) are as follows: 100 parts by weight of the thermoplastic polymer, 5 to 20 parts by weight of the component (1), 10 to 40 parts by weight of the component (2), and 2 to 3 parts of the component (3). 15 parts by weight and 5 to 20 parts by weight of the component (4). Desirable proportions of the respective components (1) to (4) are 100 parts by weight of the thermoplastic polymer, 5 to 15 parts by weight of the component (1), 10 to 30 parts by weight of the component (2), and 2 to 3 parts of the component (3). To 10 parts by weight and 5 to 15 parts by weight of the component (4).

The addition-polymerizable substance is liquid or solid at normal temperature and normal pressure within a quantitative range that does not impair properties such as photopolymerizability, and has at least one α, β-ethylenically unsaturated group in the molecule. May be included. Among such compounds, compounds having one α, β-ethylenically unsaturated group in the molecule include, for example, acrylic acid, mer acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid Examples include acrylic acid and its derivatives such as octyl, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylamide, and N-methylolacrylamide; methacrylic acid and its derivatives corresponding thereto; and styrene and vinyl esters. Examples of the compound having two α, β-ethylenically unsaturated groups in the molecule include, for example, an addition-polymerizable compound having s = 1 to 6 and s = 12 or more in the general formula [V]; In [VI], an addition polymerizable compound in which t and u are 16 or more; In the general formula [VI], an addition polymerizable compound in which t and u are 1 or more and a benzene ring is substituted with a cyclohexyl ring; 4-butanediol diacrylate,
Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate and their corresponding dimethacrylates; N, N'-methylenebisacrylamide, N,
N'-methylenebismethacrylamide, N, N'-benzylidenebisacrylamide, N, N'-benzylidenebismethacrylamide and the like are exemplified. Compounds having four or more α, β-ethylenically unsaturated groups in the molecule include:
For example, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and methacrylate corresponding thereto are exemplified. The compound having two or more α, β-ethylenically unsaturated groups in the molecule may be an oligomer, and examples of the oligomer include epoxy acrylate, oligoester acrylate, urethane acrylate, and the like. Methacrylate and the like are exemplified.

The ratio of the addition polymerizable substance 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 substance is less than 25 parts by weight, the resolution is reduced, and when it exceeds 80 parts by weight, the cold flow resistance is reduced.

The photopolymerizable composition of the present invention contains various thermoplastic polymers suitable for a development system. For example, when the development method is peeling development, as the thermoplastic polymer, chlorinated polyethylene, chlorinated polyolefin such as chlorinated polypropylene; polymethyl acrylate, polyethyl acrylate,
Acrylic polymers such as polymethyl methacrylate and polyethyl methacrylate; vinyl chloride polymers such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer; polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-acrylic Acid ester copolymers, vinylidene chloride-based polymers such as vinylidene chloride-vinyl acetate copolymers; polyvinyl acetate; saturated polyesters; polyvinyl acetals such as polyvinyl butyral and polyvinyl formal; polyisoprene; polychloroprene; Examples thereof include chlorosulfonated polyolefins such as sulfonated polypropylene; and chlorinated rubber. Preferred thermoplastic polymers for peel development are chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, and saturated polyester. One or more of these thermoplastic polymers can be used.

Further, as the solvent-developing type thermoplastic polymer, conventionally used polymers, for example, in addition to the above-described polymers, cyclized rubber,
Synthetic rubbers such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, butadiene-acrylonitrile copolymer, and fibrous materials such as polyurethane, styrene-based polymer, cellulose acetate, and nitrocellulose Polymers and the like are exemplified. One or two or more of these thermoplastic polymers can be used.

The thermoplastic polymer in the photopolymerizable composition of the present invention is preferably an alkali-soluble polymer. This alkali-soluble polymer is roughly classified into a non-styrene-based polymer containing no styrene-based monomer as a constituent unit, and a styrene-based polymer containing a styrene-based monomer as a constituent unit. Varies depending on the presence or absence of a styrene monomer.

The alkali-soluble polymer does not impair the developability, resolution, adhesion to the substrate, or peelability of the resist film, and has an appropriate acid value within a range where the resist film is resistant to an etching solution and a plating solution. I just want to. The acid value of the thermoplastic polymer differs depending on the type of the polymer. The preferred acid value of the thermoplastic polymer containing no styrene unit is 100 to 350, especially 12
The acid value of the thermoplastic polymer containing a styrene unit is from 100 to 350, preferably from 125 to 300. If the acid value of the thermoplastic polymer is less than 100, it will vary depending on the composition of the thermoplastic polymer, but generally the developability and resolution will be reduced, and if it exceeds 350, the resolution will generally be reduced.

The alkali-soluble thermoplastic polymer contained in the photopolymerizable composition has an acid addition polymerizable monomer (A) having a carboxyl group of 15 to 40% by weight, preferably 20 to 35% by weight,
It is a copolymer with 85 to 60% by weight, preferably 80 to 65% by weight of the non-acidic addition polymerizable monomer (B). A photopolymerizable composition containing such an alkali-soluble thermoplastic polymer,
Since the developing time is short and the resistance of the resist film to the developing solution is large, it is useful for forming a fine pattern.

Acid addition polymerizable monomer having a carboxyl group (A)
Examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, propionic acid, sorbic acid, and cinnamic acid, and at least one of them is used. Among the acidic addition-polymerizable monomers (A) having a carboxyl group, methacrylic acid and acrylic acid, particularly a mixture of both, are preferred. In addition, dicarboxylic acids such as maleic acid can be used as half esters or anhydrides.

The thermoplastic polymer containing the unit of the acidic addition-polymerizable monomer (A) has a property of swelling or dissolving in an alkaline liquid. Therefore, in order to impart resistance to an alkali developing solution, styrene and a derivative thereof, and a non-acidic addition-polymerizable monomer (B) such as an acrylate or a methacrylate are used as a copolymer component.

Examples of the styrene monomer include styrene; α-substituted styrene in which the α-position is substituted with an alkyl group or a halogen atom, such as α-methylstyrene and α-chlorostyrene; Substituted styrene,
For example, p-methylstyrene, p-ethylstyrene, p
-Propylstyrene, p-isopropylstyrene, p-
(Tert-butyl) styrene and the like are exemplified, and at least one kind is used. Styrene among the styrene monomers, α-
Methylstyrene and the like are preferred.

As the acrylate, an acrylate having an alkyl group having 1 to 20 carbon atoms, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-acrylate -Butyl, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, stearyl acrylate, phenyl acrylate, Examples thereof include cyclohexyl acrylate and 2-phenoxyethyl acrylate. Examples of the methacrylate include methacrylate corresponding to the above acrylate. These acrylic acid esters and methacrylic acid esters are each used alone or in combination.

In particular, the following components (A) to
The copolymerizable composition containing the alkali-soluble thermoplastic polymer composed of the copolymer (C) is hardly swelled with an alkali etchant, and is useful for imparting etching resistance.

(A) Acidic addition-polymerizable monomer 15 having a carboxyl group
(B) the following general formula [VII] (In the formula, R ¹⁹ is a hydrogen atom or a methyl group, and R ²⁰ has 1 to 1 carbon atoms.
An alkylene group of 6, 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 to 20). Weight%, and (C) relational formula [VIII] 0.25 <(QA / Qc) Exp [−eA (eA−eC)] <4.00 [VII
I] (where Q and e are Alfrey-Pr
The symbol A represents the addition-polymerizable monomer (A), and the symbol C represents the non-acidic addition-polymerizable monomer (C). And a balance of a non-acidic addition-polymerizable monomer having a Q value and an e value that satisfy the above condition.

Examples of the alkylene group for R ^{20 in} the compound represented by the general formula [VII] include methylene, ethylene, propylene, trimethylene, tetramethylene, and hexamethylene groups. Examples of the alkyl group and halogen atom for R ²¹ include the same alkyl group and halogen atom as described above.

Among the compounds represented by the general formula [VII], preferred non-acidic addition-polymerizable monomers (B) include 2-phenoxyethyl acrylate, 2-phenoxypropyl acrylate, 3-phenoxypropyl acrylate, and acrylic acid Phenoxyethoxyethyl, phenoxydiethoxyethyl acrylate, phenoxytriethoxyethyl acrylate, phenoxypropoxypropyl acrylate, phenoxydipropoxypropyl acrylate, phenoxytripropoxypropyl acrylate, ethyl (p-chlorophenoxy) acrylate, acrylic acid (P-methylphenoxy) ethyl, 2-phenoxyethyl methacrylate, 3-phenoxypropyl methacrylate, phenoxyethoxyethyl methacrylate, phenoxydiethoxyethyl methacrylate,
Phenoxytriethoxyethyl methacrylate, phenoxypropoxypropyl methacrylate, phenoxydipropoxypropyl methacrylate, phenoxytripropoxypropyl methacrylate, (p-chlorophenoxy) ethyl methacrylate, (p-methylphenoxy) ethyl methacrylate, and the like. Can be.

The unit of these non-acidic addition-polymerizable monomers (B) is contained in the copolymer at least 5% by weight, preferably 10 to 70% by weight.

Acid addition polymerizable monomer having a carboxyl group (A)
The non-acidic addition-polymerizable monomer (B) is copolymerized with the non-acidic addition-polymerizable monomer (C) satisfying the relational formula [VIII]. This non-acidic addition polymerizable monomer (C) is composed of at least one of a styrene monomer, an acrylate and a methacrylate.

When copolymerized with the non-acidic addition-polymerizable monomer (C) satisfying the above relational formula [VIII], a copolymer in which the units of the acid-addition polymerizable monomer (A) are uniformly distributed is obtained. Excellent in nature. That is, as the acid addition polymerizable monomer (A) and the non-acid addition polymerizable monomer (C), Alfrey-
In a price (Alfrey-Price) formula, the value of Q, which is an index of copolymerizability, is similar, and the use of a monomer having the opposite sign of e and a large difference in absolute value significantly increases copolymerizability. Can be. Therefore, when a monomer that does not satisfy the above relational formula [VIII] is used, a copolymer in which units of the acidic addition-polymerizable monomer (A) are unevenly distributed or a free polymer is obtained, and when the developer is developed, Poor development may occur, or in the case of extreme development, precipitation of the copolymer may occur during polymerization.

The non-acidic addition-polymerizable monomer (C) is appropriately selected according to the properties of the acidic addition-polymerizable monomer (A) as previously proposed by the present applicant (JP-A-62-153308). Reference).

When a plurality of acidic addition-polymerizable monomers (A) are used, the non-acidic addition-polymerizable monomer (C) is at least one of the acidic addition-polymerizable monomers (A). Equation [VII
I].

The non-acidic addition-polymerizable monomer (C) constitutes the remainder of the thermoplastic polymer other than the acidic addition-polymerizable monomer (A) and the non-acidic addition-polymerizable monomer (B). % By weight.

Styrene-based polymers are also excellent in resistance to etching solutions and the like, resolution and cold flow resistance. Especially,
As the styrene polymer, 15 to 40% by weight of the acidic addition-polymerizable monomer (A) having a carboxyl group, preferably
A copolymer of 20 to 35% by weight, a styrenic monomer of 1 to 35% by weight, preferably 10 to 35% by weight, an acrylate ester and a methacrylate ester of 84 to 25% by weight, preferably 70 to 30% by weight It has excellent resistance to alkali developing solutions, etching solutions and plating solutions, and also has remarkably excellent resolution and cold flow resistance.

Rather than an alkali-soluble thermoplastic polymer polymerized by combining one of the styrene-based monomer and an acrylate and a methacrylate, a styrene-based monomer, an acrylate and a methacrylate are used in combination. The photopolymerizable composition containing the alkali-soluble thermoplastic polymer polymerized by the method has excellent resolution.

To further increase the resolution, styrene-based monomers and
A combination of an acrylate having an alkyl group having 7 or more carbon atoms and a methacrylate having an alkyl group having 1 to 20 carbon atoms; a styrene-based monomer and 1 to 20 carbon atoms
An acrylate ester having an alkyl group of
Combinations with methacrylic esters having up to 3 alkyl groups are preferred. Particularly, it is preferable to use a combination of an acrylate having an alkyl group having 7 or more carbon atoms and a methacrylate having an alkyl group having 1 to 3 carbon atoms.

The ratio of the acrylate and methacrylate used together with the styrene-based monomer can be appropriately set within a range that does not lower the resolution. Acrylate / methacrylate = 20 to 65/80 to 35 %, Preferably 30-50 / 70-50% by weight.

The weight average molecular weight of the various thermoplastic polymers is usually about 10,000 to 100,000.

Incidentally, the thermoplastic polymer is usually 30 in the photopolymerizable composition.
-80% by weight, preferably 40-70% by weight. The thermoplastic polymer can be obtained by a conventional polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.

The photopolymerizable composition of the present invention may contain a stabilizer, a colorant, a plasticizer, a filler, and the like that suppress a thermal polymerization reaction and increase storage stability. Examples of the stabilizer include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol and the like, and are used in an appropriate amount as long as the photopolymerizability is not inhibited. As the coloring agent, for example, crystal violet,
Malachite green, Victoria blue, methylene blue and the like are exemplified. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate and dioctyl phthalate; fatty acid esters such as dioctyl adipate and dibutyl diglycol adipate; phosphoric acid esters such as trimethyl phosphine; Examples thereof include sulfonic amides such as acid amide. As a filler, talc,
Kaolin, calcium carbonate, barium sulfate and the like are exemplified.

The photopolymerizable composition of the present invention is generally used in the form of a liquid dissolved or dispersed in an organic solvent, preferably a photosensitive film. As the organic solvent, for example, methanol,
Alcohols such as ethanol and propanol; alicyclic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; diethyl ether and tetrahydrofuran And halogenated hydrocarbons such as methylene chloride and the like, and a mixed solvent thereof. The photosensitive film is usually
It is produced by applying a liquid photopolymerizable composition to a base film such as a polyethylene terephthalate film, drying and laminating a protective film such as a polyethylene film with a pressure roll or the like. Note that the protective film is not always necessary. In the photosensitive film, the 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 5 to 100 μm, preferably 20 to 70 μm. The photosensitive film is usually stored in a rolled state or a stacked state.

The photopolymerizable composition of the present invention is a method of applying a liquid photopolymerizable composition containing an organic solvent to a substrate, removing the organic solvent, or peeling off the protective film of the photosensitive film, if necessary. The substrate is laminated by a method of laminating the substrate film on the above substrate with a rubber roll or the like via the photosensitive layer while heating.

The photosensitive layer is exposed to a light source that generates a chemically active light beam, for example, a light source such as a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a xenon lamp. In addition, as the actinic ray, a ray having a wavelength suitable for the absorption wavelength of the photopolymerization initiator, preferably an actinic ray having a wavelength in the ultraviolet to visible region of 250 to 500 nm is mainly used. Note that electron beams, X-rays, and the like can also be used.

In the case of a photosensitive film, the exposure is usually performed by a contact exposure property in which a negative or positive pattern mask film is brought into close contact with a base film and exposed, or by a projection method.

After exposure, development is performed to form a resist image. As described above, the development can be performed by an appropriate development method according to the type of the thermoplastic resin. The peeling development is performed by peeling the base film together with the unexposed portion of the photosensitive layer. In the solvent development, a common organic solvent such as trichloroethylene and methylene chloride can be used. In the alkali development, an alkali developer containing a basic compound is used. As the basic compound, for example,
Potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium silicate, sodium phosphate, sodium pyrophosphate, alkali metal salts of pyrophosphate such as potassium pyrophosphate; butylamine, dimethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine , Triethanolamine,
Organic bases such as morpholine and pyridine are exemplified. The pH of these alkali developers is usually about 9 to 11, and an aqueous sodium carbonate solution is preferably used. In the developer,
Organic solvents such as ethylene glycol monobutyl ether,
A surfactant, an antifoaming agent and the like may be contained.

In the manufacture of printed wiring boards, after using a resist image as a mask and treating with a plating solution or an etching solution,
The resist image is removed with a strong alkaline aqueous solution, for example, a 2 to 10% by weight aqueous sodium hydroxide solution.

The photopolymerizable composition of the present invention is useful as a photoresist for producing a printed wiring board, a circuit board, a metal relief image, a printing plate, and the like.

[Effect of the Invention] The photopolymerizable composition of the present invention comprises (a) a sulfide compound represented by the general formula [I], (b) a benzophenone compound, and (c) an alkylaminobenzophenone compound. Since it contains at least a photopolymerization initiator obtained by combining (d) a 2,4,5-triarylimidazolyl dimer and (e) a triarylmethane leuco dye, it has excellent photopolymerizability.

In addition, a photopolymerizable composition containing at least the compound represented by the general formula [IV] as an addition polymerizable substance has a short resist film stripping time and can prevent alkali burning.

Further, the thermoplastic polymer is an alkali-soluble polymer, particularly a photopolymerizable composition having an acid value of 100 to 350, in addition to the above-described properties, is alkali-developable, alkali-developer-resistant, etchant-resistant, and alkali-resistant. It has excellent plating solution properties and is useful for forming fine patterns.

Further, the thermoplastic polymer has an acid addition-polymerizable monomer having a carboxyl group of 15 to 40% by weight, and a compound represented by the general formula [VI
At least 5 of the non-acidic addition-polymerizable monomer represented by formula (I)
The photopolymerizable composition, which is a copolymer of the non-acidic addition-polymerizable monomer having a Q value and an e value satisfying the relational formula [VIII], further imparts etching resistance. Useful in

Further, the thermoplastic polymer has an acid addition polymerizable monomer having a carboxyl group of 15 to 40% by weight,
The photopolymerizable composition, which is a copolymer of 35% by weight and 84 to 25% by weight of an acrylic ester and / or a methacrylic ester, has particularly excellent resolution and cold flow resistance in addition to the above properties.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples.

Examples 1 to 4 and Comparative Examples 1 to 4 The following components were mixed to obtain a solution A.

Copolymer of 20% by weight of methacrylic acid, 60% by weight of methyl methacrylate and 20% by weight of butyl acrylate (acid value 130) 50 g Trimethylolpropane triacrylate 15 g 2,2'-bis (4-acryloyldiethoxyphenyl) ) Propane 10 g Diamond green GH 0.03 g Methyl ethyl ketone 70 g Tetrahydrofuran 20 g To this solution A, a photopolymerization initiator was mixed at a ratio shown in Table 8 to obtain a photopolymerizable composition. Photopolymerizable composition, thickness 25
The composition was applied to a base film made of a polyethylene terephthalate film having a thickness of μm and dried at a temperature of 75 ° C. to produce a photosensitive film. The thickness of the photosensitive layer was 50 μm. The photosensitive film was laminated on the polished copper-clad laminate using a rubber roller heated to 100 ° C. A 21-step Stofa step tablet is superimposed on the base film, irradiated with a 2 Kw ultra-high pressure mercury lamp from a distance of 50 cm for 10 seconds and cured, then the base film is peeled off, and 70% with a 1% aqueous solution of sodium carbonate at 30 ° C. Spray development was performed for 2 seconds to form a resist image.
This resist image is formed corresponding to the step tablet in which the amount of transmitted light changes stepwise. Therefore, the photopolymerizability was determined based on the number of steps of the step tablet corresponding to the minimum exposure required for forming a resist image. In addition,
The larger the number indicating the number of steps of the step tablet, the higher the sensitivity of the photopolymerizable composition.

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

 Table 8 shows the results together with the composition of the photopolymerization initiator.

As is clear from Table 8, when the photopolymerization initiator of each example was used, the composition was cured in a shorter time than in Comparative Examples 1 to 4.
In addition, the resist images obtained from the photopolymerizable compositions of Examples 1 to 4 all showed sufficient resistance to an etching solution and a plating solution.

Examples 5 to 11 and Comparative Examples 5 to 7 Solutions B were prepared by mixing the following components.

A copolymer of 20% by weight of methacrylic acid, 60% by weight of methyl methacrylate, and 20% by weight of isobutyl acrylate (acid value 13
0) 50 g 4-benzoyl-4'-methyldiphenyl sulfide 0.8 g ethyl p- (dimethylamino) benzoate 0.6 g benzophenone 2.0 g 4,4'-bis (diethylamino) benzophenone 0.2 g 2,2'-di (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole 1.5 g leuco crystal violet 0.3 g methyl ethyl ketone 70 g tetrahydrofuran 20 g This solution B was mixed with an addition polymerizable substance in the ratio shown in Table 9 to obtain light. A polymerizable composition was obtained. In Table 9, “Compound No.” indicates the number of the phthalic acid derivative shown in Tables 1 to 7.

Then, a photosensitive film was prepared in the same manner as in Example 1, and the curing time of the photopolymerizable composition was measured. Further, the minimum time required for development was measured by the same spray development as in Example 1. Furthermore, the copper-clad laminate on which the resist image is formed is etched with a cupric chloride etching solution,
After the treatment with the plating solution, it was immersed in a 2% by weight aqueous solution of sodium hydroxide at a temperature of 50 ° C., and the time until the resist image was peeled was measured. Table 9 shows the results.

As is clear from Table 9, the photopolymerizable compositions of Comparative Examples 5 to 7 do not have sufficient photopolymerizability, developability, or any of the properties of resist image releasability. On the other hand, it was found that the photopolymerizable compositions of Examples 5 to 11 can be photopolymerized in a short time, can be developed in a short time, and the resist image peels off in a short time. The resist images of Examples 5 to 11 all showed sufficient resistance to an etching solution and a plating solution.

Example 12 The following components were mixed to obtain a photopolymerizable composition.

10% by weight of methacrylic acid, 15% by weight of acrylic acid, 52% by weight of methyl methacrylate, 2-ethylhexyl acrylate
23% by weight of copolymer (acid value 182) 50 g Compound No. 6 30 g 4-benzoyl-4'-methyldiphenyl sulfide
0.8 g ethyl p- (dimethylamino) benzoate 0.6 g benzophenone 2.0 g 4,4'-bis (diethylamino) benzophenone 0.2 g 2,2'-di (2-chlorophenyl) -4,4 ', 5,5'- Tetraphenylbisimidazole 1.5 g Leuco crystal violet 0.3 g Victoria blue GH 0.1 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g Example 13 Instead of the copolymer of Example 12, methacrylic acid 20% by weight, methyl methacrylate 45% by weight, acrylic A photopolymerizable composition was prepared in the same manner as in Example 12, except that 50 g of a copolymer (acid value 130) of 35% by weight of 2-phenoxyethyl acid was used.

Example 14 A copolymer 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 acrylate (acid value 200 ) A photopolymerizable composition was prepared in the same manner as in Example 12 except that 50 g was used.

Example 15 Instead of the copolymer of Example 12, a copolymer 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 was used. Other than using 50g of coalescing (acid value 200),
A photopolymerizable composition was prepared in the same manner as in Example 12.

Example 16 Instead of the copolymer of Example 12, 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 10% by weight of styrene, 22% by weight of 2-ethylhexyl acrylate, methyl methacrylate
Example 1 except that 40% by weight of the copolymer (acid value 200) was used
A photopolymerizable composition was prepared in the same manner as in 2.

Example 17 Instead of the copolymer of Example 12, 14% by weight of methacrylic acid, 14% by weight of acrylic acid, 25% by weight of styrene, 17% by weight of 2-ethylhexyl acrylate, methyl methacrylate
Example 1 except for using 30% by weight of copolymer (acid value 200)
A photopolymerizable composition was prepared in the same manner as in 2.

Example 18 Instead of the copolymer of Example 12, 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) A photopolymerizable composition was prepared in the same manner as in Example 12, except for using.

Example 19 Addition polymerizable substance (compound) of the photopolymerizable composition of Example 12
No. 6) Instead of 30 g, use 4 g of compound No. 22, 11 g of trimethylolpropane triacrylate, 4 g of 2,2'-bis (4-acryloyldiethoxyphenyl) propane, and 3 g of nonaethylene glycol dimethacrylate. A photopolymerizable composition was prepared in the same manner as in Example 12, except for the above.

Comparative Example 8 Instead of the copolymer of Example 12, a copolymer of 6% by weight of methacrylic acid, 6% by weight of acrylic acid, 30% by weight of styrene, 17.5% by weight of 2-ethylhexyl acrylate, and 40.5% by weight of methyl methacrylate was used. A photopolymerizable composition was prepared in the same manner as in Example 12, except that the combined compound (acid value: 85.5) was used.

Comparative Example 9 Instead of the copolymer of Example 12, a copolymer of 28% by weight of methacrylic acid, 30% by weight of styrene, 17% by weight of 2-ethylhexyl methacrylate, and 25% by weight of methyl methacrylate (acid value 200) A photopolymerizable composition was prepared in the same manner as in Example 12, except for using.

Then, in the same manner as in Example 1, a photosensitive film was prepared, and the sensitivity of the photopolymerizable composition and the stripping time of the resist image were evaluated, and the resolution, resistance to alkali solution, and cold flow resistance were evaluated as follows. Was evaluated as follows.

(1) Resolution evaluation method As a pattern mask, 10 µm to 150 µm in 10 µm steps
Spray development, washing and drying were carried out in the same manner as in Example 1 above, using a set of five silver salt pattern masks each having a line width of m and a space having an area ratio of 1: 1. Then, observe the resist image with an optical microscope with a magnification of 200 times,
The minimum mask line width without line meandering and with no resist bridge in the space is expressed as the resolution.

(2) Evaluation Method for Resistance to Alkaline Solution Exposure was performed under the same conditions as in Example 1 without using the above pattern mask to form a resist film. The resist film was immersed in a 1% by weight aqueous solution of sodium carbonate adjusted to pH 8.5 for 1 hour, and the resistance to the alkali solution was visually determined. The resistance to an alkali solution was evaluated according to the following criteria.

Excellent: No change in resist film Good: Slight swelling of resist film (3) Evaluation method for cold flow resistance A 20 μm-thick polyethylene film was laminated on the photosensitive layer of the photosensitive film, and wound up while applying tension. , To prepare a wound dry film. The wound dry film was set up and stored at room temperature, and the period until the photopolymerizable composition leaked from the edge of the dry film was examined based on the following criteria, and was used as an index of cold flow resistance.

Excellent: 6 months or more Good: 1 to 4 months The results obtained are shown in Table 10.

As shown in Table 10, as compared with the photopolymerizable compositions of Comparative Examples 8 and 9, the photopolymerizable compositions of Examples 12 to 19 were photopolymerizable, resist image peelability, resolution and alkali solution. Excellent resistance and good cold flow resistance. The resist images of Examples 12 to 19 all showed sufficient resistance to an etching solution and a plating solution.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 2/46-2/50 C08F 4/00 C08F 290/06 G03F 7/028-7/031

Claims (15)

(57) [Claims] 1. A photopolymerizable composition containing a photopolymerization initiator, a thermoplastic polymer, and a liquid or solid addition polymerizable substance at normal temperature and pressure, wherein the photopolymerization initiator comprises: (a) Sulfide compound represented by general formula [I] (Wherein R ¹ , R ² and R ³ are the same or different,
A group selected from the group consisting 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;
Represents an integer of 1 to 5, and m represents an integer of 1 to 4. (B) a benzophenone-based compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group; c) an alkylaminobenzophenone-based compound optionally having a substituent selected from the group consisting of a halogen atom, an alkyl group, an optionally substituted aryl group, an alkoxycarbonyl group, and an alkoxy group; A photopolymerizable composition comprising at least a 2,4,5-triarylimidazolyl dimer which may have a substituent and (e) a triarylmethane leuco dye. 2. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator contains an alkyl p- (dialkylamino) benzoate. 3. The photopolymerizable composition according to claim 1, wherein the alkylaminobenzophenone compound is 4,4'-bis (dialkylamino) benzophenone. 4. An addition polymerizable substance 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 and R ⁹ are the same or different and represent a linear or branched alkylene group, R ¹¹ is a hydrogen atom, a halogen The photopolymerizable compound according to claim 1, wherein the photopolymerizable compound contains at least a compound represented by an atom or an alkyl group having 1 to 10 carbon atoms, p and q each represent an integer of 1 to 10, and r represents an integer of 1 to 20. Composition. 5. The photopolymerizable composition according to claim 4, wherein the addition polymerizable substance contains a (meth) acrylate having three (meth) acryloyl groups in a molecule. 6. An addition polymerizable substance represented by the following general formula [V]: (Wherein, R ¹² , R ¹³ and R ¹⁴ are the same or different and each represent a hydrogen atom or a methyl group, and s represents an integer of 7 to 11). Polymerizable composition. 7. An addition polymerizable substance represented by the following general formula [VI]: (Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different,
The photopolymerizable composition according to claim 4, which comprises a compound represented by the following formula: wherein a hydrogen atom or a methyl group is represented, and t and u each represent an integer of 1 to 15. 8. The polymerizable composition according to claim 1, wherein the thermoplastic polymer is an alkali-soluble polymer. 9. The photopolymerizable composition according to claim 1, wherein the thermoplastic polymer has an acid value of 100 to 350. 10. A thermoplastic polymer comprising: (A) an acid addition polymerizable monomer 15 having an alkoxyl group;
(B) the following general formula [VII] (In the formula, R ¹⁹ is a hydrogen atom or a methyl group, and R ²⁰ has 1 to 1 carbon atoms.
An alkylene group of 6, 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 to 20). % By weight, and (C) Relational formula [VIII] 0.25 <(QA / Qc) Exp [−eA (eA−eC)] <4.00 [VII
I] (where Q and e are Alfrey-Pr
The symbol A represents the addition-polymerizable monomer (A), and the symbol C represents the non-acidic addition-polymerizable monomer (C). 9. The photopolymerizable composition according to claim 8, which is a copolymer of a non-acidic addition polymerizable monomer having a Q value and an e value satisfying the following. 11. A thermoplastic polymer comprising 15 to 40% by weight of an acid addition polymerizable monomer having a carboxyl group, 1 to 35% by weight of a styrene monomer, 84 to 25% by weight of an acrylate and a methacrylate. The photopolymerizable composition according to claim 8, which is a copolymer with%. 12. The photopolymerizable composition according to claim 1, comprising 25 to 80 parts by weight of an addition polymerizable substance and 0.1 to 30 parts by weight of a photopolymerization initiator based on 100 parts by weight of the thermoplastic polymer. 13. The photopolymerization initiator may have (a) a halogen atom, an alkyl group, or a substituent, based on 100 parts by weight of the compound represented by the above general formula [I]. 50 to 500 parts by weight of a benzophenone-based compound which may have a substituent selected from the group consisting of an aryl group, an alkoxycarbonyl group and an alkoxy group, (c) a halogen atom, an alkyl group, 5 to 250 parts by weight of an alkylaminobenzophenone-based compound which may have a substituent selected from the group consisting of an aryl group, an alkoxycarbonyl group and an alkoxy group, and (d) may have a substituent 13. The photopolymerizable composition according to claim 1 or 12, comprising 50 to 400 parts by weight of a 2,4,5-triarylimidazolyl duplex and 10 to 70 parts by weight of (e) a triarylmethane leuco dye. 14. The photopolymerization initiator further comprises (a) 25 to 200 parts by weight of an alkyl p- (dialkylamino) benzoate per 10 parts by weight of the compound represented by the above general formula [I]. 13. The photopolymerizable composition according to claim 12, wherein 15. An addition-polymerizable substance is 5 to 20 parts by weight of a compound represented by the general formula [IV], based on 100 parts by weight of a thermoplastic polymer, and three (meth) acryloyl groups in a molecule. 10 to 40 parts by weight of a (meth) acrylate having the formula: 2 to 15 parts by weight of a compound represented by the general formula [V]; and 5 to 20 parts by weight of a compound represented by the general formula [VI]. 13. The photopolymerizable composition according to claim 1 or 12.