JP2000321766A - Photopolymerizable composition, photopolymerizable image forming material and negative image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition and a photopolymerizable image forming material having high sensitivity to light in the IR region, in particular infrared laser light and capable of directly forming a pattern with semiconductor laser or YAG laser and to provide a negative image forming method. SOLUTION: The photopolymerizable composition contain (A) an ethylenically unsaturated compound, (B) an IR absorbing dye which does not generate an active radical and (C) an α-aminoacetophenone derivative. A layer of the photopolymerizable composition is formed on the surface of a substrate to obtain the objective photopolymerizable image forming material. The photopolymerizable image forming material is imagewise exposed with <=500 mj/cm2 infrared laser light and developed with an aqueous alkali solution to form the objective negative image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate, a color proof for print proofing, a color filter resist for a liquid crystal display or a plasma display, a photoresist for an integrated circuit of a semiconductor device, a copper etching resist for a wiring board or gravure plate making, and the like. Used in, the photopolymerizable composition and photopolymerizable image forming material having high sensitivity to light mainly in the infrared region, and a negative image forming method, particularly suitable for direct drawing by a semiconductor laser or YAG laser, etc. The present invention relates to a photopolymerizable composition, a photopolymerizable image forming material, and a negative image forming method.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an image by exposing a photopolymerizable composition, for example, a photopolymerizable composition comprising an ethylenically unsaturated compound and a photopolymerization initiator, or further comprising an organic polymer binder, etc. A method of forming a cured relief image by dissolving and removing non-exposed portions after imagewise exposing to polymerize and cure the ethylenically unsaturated compound in exposed portions, forming a layer of After causing a change in the adhesive strength of the polymerizable composition layer to the support, a method of forming an image by peeling the support, and a change in toner adhesion of the photopolymerizable composition layer due to light. Various methods such as an image forming method used are known.

On the other hand, formation of an image using these conventional photopolymerizable compositions is not sufficiently sensitive to light in a long wavelength region of 500 nm or more, especially 600 nm or more. On the other hand, with the remarkable progress of semiconductor lasers and the like, a near-infrared laser light source in a long wavelength region of 700 to 1300 nm has been easily used, and an image forming method using these laser lights, especially digital Direct drawing which directly obtains an image from information has attracted attention. For example, as a photopolymerization initiator system, a photopolymerizable composition containing a boron anion-containing salt dye (for example, JP-A-62-143044, JP-A-62-1630).
No. 150242, JP-A-5-5988, JP-A-5-1
97069, each gazette. ), A photopolymerizable composition containing a specific cyanine dye and an s-triazine compound (see, for example, JP-A-4-31863), and a specific squarylium dye and an s-triazine compound. Photopolymerizable composition (for example, see JP-A-6-4363).
See No. 3 publication. ) Etc. have been proposed.

However, these photopolymerizable compositions proposed to be sensitive to near-infrared laser light are also disclosed in
The sensitivity is remarkably low for light in the infrared region exceeding nm, and a high-output laser is required for exposure to use the heat of near-infrared light.
Direct writing with an AG laser or the like was difficult.

On the other hand, JP-A-9-230126 discloses (a) a photopolymerizable acrylic resin having a polymerizable unsaturated group, (b) an ethylenically unsaturated compound, (c) a color pigment, and (d) A near-infrared photosensitive coloring composition for a color filter, comprising a cationic dye-borate anion complex, and (e) a photopolymerization initiator other than the complex (d) is described. As an initiator, for example, JP-A-6
Although α-aminoacetophenone derivatives known from JP-A-3-264560 and JP-A-6-16713 are used, according to the study of the present inventors, the described composition has remarkably high sensitivity. It was found that the density was not so high that it could not be directly drawn by a semiconductor laser or a YAG laser.

In the case of the composition described in JP-A-9-230126, the cationic dye-borate anion complex of component (d), which is an infrared absorbing dye, itself has a radical generating ability and is used in combination. The photopolymerization initiator other than the component (d), such as the α-aminoacetophenone derivative, of the component (e) is said to be activated by the action of the radical generated by the component (d) to generate a radical. That is, the publication discloses a specific infrared absorbing dye having a radical generating ability,
It merely discloses the combined use of a photopolymerization initiator that generates a radical when it coexists.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and accordingly, the present invention has a high sensitivity to light in the infrared region, particularly to infrared laser light. It is another object of the present invention to provide a photopolymerizable composition, a photopolymerizable image forming material, and a negative image forming method that can be directly drawn by a semiconductor laser, a YAG laser, or the like.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a photopolymerization containing an ethylenically unsaturated compound, a specific infrared absorbing dye, and a specific photopolymerization initiator. The present invention has been completed by finding that the hydrophilic composition can achieve the above object, that is, the present invention provides a light-emitting composition comprising the following components (A), (B), and (C). The gist is a polymerizable composition. (A) Ethylenically unsaturated compound (B) Infrared absorbing dye that does not generate active radicals by itself (C) α-Aminoacetophenone derivative

The present invention also provides a photopolymerizable image forming material comprising a support and a layer comprising the photopolymerizable composition formed on the surface of the support.
And after exposing the photopolymerizable image forming material to an image with an exposure amount of 500 mj / cm ² or less by infrared laser light,
And a negative image forming method of developing with an aqueous alkali solution.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylenically unsaturated compound (A) constituting the photopolymerizable composition of the present invention will be described later (C) when the photopolymerizable composition is irradiated with actinic rays. )
It is a compound having an ethylenically unsaturated double bond which undergoes addition polymerization by the action of the component α-aminoacetophenone derivative, and in some cases crosslinks and cures.

In the present invention, a preferable ethylenically unsaturated compound is, for example, (meth) acrylic acid (in the present invention, “(meth) acryl” means acryl and methacryl). , Crotonic acid, isocrotonic acid, maleic acid, itaconic acid, unsaturated carboxylic acids such as citraconic acid and ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, Compatibility with aliphatic polyhydroxy compounds such as tetramethylene glycol, neopentyl glycol, hexamethylene glycol, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and sorbitol Bonic esters, specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate A) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate , Trimethylolethanetri (meta)
Acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tet (Meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate And similar crotonates, isocrotonates, maleates, itaconates, citraconates and the like.

Suitable ethylenically unsaturated compounds include, for example, fatty acids such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, dimer acid diisocyanate, lysine ester triisocyanate, undecatriisocyanate, hexamethylene triisocyanate and the like. Alicyclic polyisocyanates such as aromatic polyisocyanates, cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate;
Polyisocyanate compounds such as aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, tris (isocyanate phenyl methane), and tris (isocyanate phenyl) thiophosphate; Urethane (meth) by reaction with hydroxy (meth) acrylate compounds such as (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolethane tri (meth) acrylate ) Acrylates, specifically, for example, hexamethylenebis [(meth) acrylo Loxymethylurethane], hexamethylenebis [(meth) acryloyloxyethylurethane], hexamethylenebis {tris [(meth) acryloyloxymethyl] methylurethane}, hexamethylenebis {tris [(meth) acryloyloxymethyl] ethyl Urethane and the like.

Further, as preferred ethylenically unsaturated compounds, for example, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol Polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, etc. Heterocyclic polyethers such as aliphatic polyepoxy compounds, triglycidyl isocyanurate and triglycidyl tris (2-hydroxyethyl) isocyanurate A polyepoxy compound such as an aromatic polyepoxy compound such as a xy compound, a phenol novolak polyepoxy compound, an (o-, m-, p-) cresol novolak polyepoxy compound, a bisphenol A polyepoxy compound, and a bisphenol F polyepoxy compound; Epoxy (meth) acrylates obtained by reaction with (meth) acrylic acid and the like can be mentioned.

Further, as suitable ethylenically unsaturated compounds, for example, amides obtained by reacting the above unsaturated carboxylic acids with aliphatic polyamine compounds such as methylene diamine, ethylene diamine, diethylene triamine, hexamethylene diamine, etc. Specific examples include methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, diethylenetriaminetris (meth) acrylamide, and hexamethylenebis (meth) acrylamide.

Examples of the ethylenically unsaturated compound other than the above include, for example, alkyl esters of unsaturated carboxylic acids as described above, hydroquinone di (meth) acrylate,
Esters of an aromatic polyhydroxy compound such as resorcinol di (meth) acrylate and pyrogallol tri (meth) acrylate with an unsaturated carboxylic acid, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) ) (Meth) acrylic phosphate compounds such as acryloyloxyethylene glycol phosphate, (meth) acryloylethylene oxide adduct of ethylene glycol,
(Meth) acryl hydroxy compounds such as (meth) acryloyl diethylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane, and condensates of ethylene glycol, (meth) acrylic acid and phthalic acid, diethylene glycol Such as condensates of (meth) acrylic acid and maleic acid, condensates of pentaerythritol, (meth) acrylic acid and terephthalic acid, and condensates of butanediol, glycerin, (meth) acrylic acid and adipic acid Condensates of a hydroxy compound, an unsaturated carboxylic acid and a polyvalent carboxylic acid, and the like can be given.

(B) Constituting the Photopolymerizable Composition of the Invention
The infrared absorbing dye of the component has an absorption band in the infrared region having a wavelength of 700 to 1300 nm, efficiently absorbs light in the wavelength region, and uses the light excitation energy to generate the α component (C).
A compound having a sensitizing function of spectrally sensitizing aminoacetophenone to generate an active radical which induces polymerization of the ethylenically unsaturated compound as the component (A). It is essential that the absorbing dye does not generate active radicals by itself, and if it does generate active radicals, it is difficult to achieve the object of the present invention.

Here, that the active radical is not generated by itself means that the infrared absorbing dye of the component (B) alone has no ability to induce the polymerization of the ethylenically unsaturated compound of the component (A). However, this does not mean that decomposition does not occur at all by infrared irradiation.

In the present invention, such an infrared absorbing dye is described, for example, in "Functional Dye Chemistry" (edited by Higaki, 19
1981, published by CMC Co., Ltd.), "Specially-functional dyes"
(Edited by Ikemori and Hashiya, 1986, published by CMC Inc.), “Dye Handbook” (edited by Okawa, Hirashima, Matsuoka, Kitao, published by Kodansha), Exciton Inc. Is 19
It can be selected from near-infrared absorbing dyes described in a laser dye catalog issued in 1989, a catalog issued by the Japan Photographic Dye Laboratories in 1995, etc. Specifically, for example, phthalocyanine-based dyes, porphyrins Nonionic dyes having no quaternary ammonium salt structure, such as, pentacene, Ni thio complex, anthraquinone, and phenanthroline, and cyanine, merocyanine, carbocyanine, rhodamine, and azomethine ,
Azurenium-based, polymethine-based, indoline-based, thiazine-based, xanthene-based, acridine-based, oxazine-based, and the like, such as a dye having a quaternary ammonium salt structure and having a counter anion that is not an organic boron anion. Among them, the former nonionic dyes are preferable, and phthalocyanine dyes are particularly preferable.

Examples of the phthalocyanine-based infrared absorbing dye include, for example, JP-A-64-60660 and JP-A-1-1-1.
00171, JP-A-3-31247, JP-A-4-1
5263, JP-A-4-15264, JP-A-4-15
265, JP-A-4-15266, alkyl phthalocyanine compounds described in JP-A-2-138382,
Acyloxyphthalocyanine compounds described in JP-A-77840 and JP-A-3-100066;
No. 348168, alkoxy phthalocyanine compounds described in JP-A-60-23451,
JP-A-215662, JP-A-61-215663, JP-A-63-270765, JP-A-1-287175, JP-A-2-43269, JP-A-2-296885, JP-A-3-43461, JP-A-3-43 Naphthalocyanine compounds described in JP-A-265664 and JP-A-3-265665; JP-A-1-108264;
And dinaphthalocyanine compounds described in each of the publications No. 108265.

Particularly preferred among these are phthalocyanines
System infrared absorbing dye has an absorption maximum (λ _max) To 750-1
It has a wavelength range of 200 nm, and specifically,
For example, a compound having the following structure may be mentioned.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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(C) Constituting the Photopolymerizable Composition of the Invention
The α-aminoacetophenone derivative of the component generates an active radical by sensitization of the infrared absorbing dye of the component (B) and induces polymerization of the ethylenically unsaturated compound of the component (A). In the above, those represented by the following general formula (I) are preferable.

[0028]

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[In the formula (I), R ¹ represents an alkyl group which may have a substituent, an allyl group which may have a substituent, a phenyl group which may have a substituent, Or a benzyl group which may have a substituent; R ² represents an alkyl group which may have a substituent, an allyl group which may have a substituent, or a group which has a substituent; R ³ and R ⁴ each independently represent an alkyl group which may have a substituent, an allyl group which may have a substituent, or a group which has a substituent. A phenyl group or a benzyl group which may have a substituent, and R ³ and R ⁴
May be connected to each other, or R ³ or R ⁴ and R ¹ or R ² may be connected to each other to form a cyclic structure, and the benzene ring may have a substituent. ]

Here, R ¹ in the general formula (I),
The alkyl group of R ² , R ³ and R ⁴ has 1 carbon atom.
To 15, particularly preferably 1 to 10. Further, as a substituent in an alkyl group, an allyl group, a phenyl group, and a benzyl group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acetoxyalkoxy group, an alkoxyalkoxy group, an alkylcarbonylalkyl group, a benzyl group, Examples thereof include an alkylthio group, a haloalkyl group, and a halogen atom. Also, R ³ and R
⁴ are linked to each other, or R ³ or R ⁴ and R ¹
Alternatively, the cyclic structure formed by linking R ² to each other includes pyrrolidine, piperidine, piperazine, morpholine, oxazolidine, pyridine and the like.

As the substituent on the benzene ring,
Alkyl group, hydroxy group, alkoxy group, allyloxy group, phenoxy group, benzoyl group, silyloxy group,
Mercapto group, alkylthio group, allylthio group, cycloalkylthio group, benzylthio group, phenylthio group, alkylsulfonyl group, phenylsulfonyl group, alkylsulfinyl group, alkylamino group, allylamino group,
A pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a halogen atom, and the like, and the benzene ring may form a condensed ring.As the condensed ring, fluorenone, dibenzosuberone, indoline, quinoxaline, Carbazole, phenazine, acridanone, benzodioxole, benzofuran, xanthene,
Xanthone, phenoxazine, benzothiazole, phenothiazine and the like can be mentioned.

As the α-aminoacetophenone derivative represented by the above general formula (I), the following compounds may be specifically mentioned according to the basic skeleton of the compound and the number of carbon atoms. Of these, particularly preferred are those in which R ¹ is a methyl group or a benzyl group, R ² is an ethyl group or an allyl group, and R ³ and R ⁴ are each a methyl group or linked to each other to form a cyclic structure. The compound is a morpholino group formed, wherein the benzene ring is unsubstituted or a methylthio group, a dimethylamino group, or a morpholino group as a substituent.

Propane classified into C3 of the basic skeleton
As 1-one, 1-phenyl-2-dimethylamino-
2-methyl-3- (4-methylphenyl) -propane-
1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methoxyphenyl) -propane-1-
On, 1-phenyl-2-dimethylamino-2-methyl-3- (3,4-dimethoxyphenyl) -propane-1
-One, 1-phenyl-2-dimethylamino-2-methyl-3- (4-methylthiophenyl) -propane-1-
On, 1-phenyl-2-dimethylamino-2-methyl-3- (4-fluorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-
3- (2-chlorophenyl) -propan-1-one, 1
-Phenyl-2-dimethylamino-2-methyl-3-
(4-chlorophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-
Bromophenyl) -propan-1-one, 1-phenyl-2-dimethylamino-2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1-phenyl-
2-dimethylamino-2-benzyl-propan-1-one, 1,3-diphenyl-2-dimethylamino-2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2-dimethylamino- 2-benzyl-propan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-
1-one, 1- (4-benzoylphenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1-
(4-methylthiophenyl) -2-dimethylamino-2
-Methyl-3- (4-methylphenyl) -propane-1
-One, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-methoxyphenyl)
-Propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (3,4
-Dimethoxyphenyl) -propan-1-one, 1-
(4-methylthiophenyl) -2-dimethylamino-2
-Methyl-3- (4-fluorophenyl) -propane-
1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (2-chlorophenyl)
-Propan-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-3- (4-chlorophenyl) -propan-1-one, 1- (4-methylthiophenyl) -2- Dimethylamino-2-methyl-
3- (4-bromophenyl) -propan-1-one, 1
-(4-methylthiophenyl) -2-dimethylamino-
2-methyl-3- (4-benzoylphenyl) -propan-1-one, 1,3-bis (4-methylthiophenyl) -2-dimethylamino-2-methyl-propane-1
-One, 1- (4-butylthiophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propane-1
-One, 1- (4-cyclohexylthiophenyl) -2
-Dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (4-benzylthiophenyl)-
2-dimethylamino-2-benzyl-propan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-propan-1-one, 1-
(4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one,
1- (4-morpholinophenyl) -2-dimethylamino-2- (2-chloropentenyl) -propan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-propane-1 -ON, 1- (4-
Morpholinophenyl) -2-dimethylamino-2-benzyl-3-phenyl-propan-1-one, 1- (N-
Methylindoline-5-yl) -2-dimethylamino-
2-benzyl-propan-1-one, 1- (N-butylphenoxazin-2-yl) -2-morpholino-2-benzyl-propan-1-one and the like.

Butane-1 classified into carbon number 4 of the basic skeleton
-One as 1-phenyl-2-dimethylamino-2
-Benzyl-butan-1-one, 1- (4-methylphenyl) -2-dimethylamino-2-benzyl-butane-
1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1-
(3,5-dimethyl-4-methoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1-
(3,4-dimethoxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4,5
-Trimethoxyphenyl) -2-dimethylamino-2-
Benzyl-butan-1-one, 1- (4-hydroxyphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-dimethylamino -2-benzyl-butan-1-one, 1- (4-allyloxyphenyl) -2-
Dimethylamino-2-benzyl-butan-1-one, 1
-(4-ethoxycarbonylmethoxyphenyl) -2-
Dimethylamino-2-benzyl-butan-1-one, 1
-[4- (1,1,2-trimethylpropyldimethylsilyloxy) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2 -Benzyl-butane-1
-One, 1- (4-chlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,4
-Dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (3,4-dichlorophenyl) -2-dimethylamino-2-benzyl-butane-
1-one, 1- (3,5-dichlorophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1-
(4-bromophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-mercaptophenyl) -2-dimethylamino-2-benzyl-butane-
1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1-
(4-methylthiophenyl) -2-dibutylamino-2
-Benzyl-butan-1-one, 1- (4-methylthiophenyl) -2-di (2-methoxyethyl) amino-2
-Benzyl-butan-1-one, 1- [4- (2-methoxyethylthio) phenyl] -2-dimethylamino-2
-Benzyl-butan-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-dimethylamino-
2-benzyl-butan-1-one, 1- (4-octylthiophenyl) -2-dimethylamino-2-benzyl-
Butan-1-one, 1- (4-methylsulfonylphenyl) -2-dimethylamino-2-benzyl-butan-1
-One, 1- [4- (4-methylphenylsulfonyl)
Phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-benzenesulfonylphenyl) -2-dimethylamino-2-benzyl-butane-1
-One, 1- (4-methylsulfinylphenyl) -2
-Dimethylamino-2-benzyl-butan-1-one,
1- (4-aminophenyl) -2-dimethylamino-2
-Benzyl-butan-1-one, 1- (4-methylaminophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl)
-2-dimethylamino-2-benzyl-butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-methylbenzyl) -butan-1-
On, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one, 1- (4-dimethylaminophenyl)-
2-dimethylamino-2- (4-dodecylbenzyl)-
Butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2- (1-chlorohexenylmethyl) -butan-1-one, 1- (4-dimethylaminophenyl) -2-dimethyl Amino-2- (2-pinen-10-yl) -butan-1-one, 1- (4-dimethylamino-2-methylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1 -(4-dimethylamino-3-ethylphenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-diethylaminophenyl) -2-dimethylamino-2-benzyl-butan-1- On, 1- (4-isopropylaminophenyl) -2-dimethylamino-2-butyl-butan-1-one, 1- [4- (2-methoxyethylamino) phenyl] -2- Methylamino-2-benzyl -
Butan-1-one, 1- [4- (3-methoxypropylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-acetylaminophenyl) -2-dimethylamino -2-benzyl-butane-
1-one, 1- [4- (N-acetylmethylamino) phenyl] -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (N-acetyl-3-methoxypropylamino) Phenyl] -2-dimethylamino-2
-Benzyl-butan-1-one, 1- (4-piperidinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-
Dimethylamino-2-benzyl-butan-1-one, 1
-(4-morpholinophenyl) -2-dimethylamino-
2- (3,4-dimethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-ethylbenzyl) -butan-1-one, 1- (4 -Morpholinophenyl) -2-dimethylamino-2- (4-isopropylbenzyl) -butane-1
-One, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-butylbenzyl) -butane-1-
On, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-isobutylbenzyl) -butane-1
-One, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -butane-1
-One, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-hydroxymethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2
-Dimethylamino-2- (4-acetoxyethylbenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-methoxybenzyl) -butan-1-one, -(4-morpholinophenyl) -2-dimethylamino-2- (4-butoxybenzyl) -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- Hydroxyethoxy) benzyl] -butan-1-one, 1- (4
-Morpholinophenyl) -2-dimethylamino-2-
[4- (2-methoxyethoxy) benzyl] -butane-
1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2- (2-methoxyethoxy) ethoxy) benzyl] -butan-1-one, 1-
(4-morpholinophenyl) -2-dimethylamino-2
-[4- (2- (2-methoxyethoxy) ethoxycarbonyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4-
(2- (2- (2-methoxyethoxy) ethoxycarbonyl) ethyl) benzyl] -butan-1-one, 1-
(4-morpholinophenyl) -2-dimethylamino-2
-[4- (2-bromoethyl) benzyl] -butane-1
-One, 1- (4-morpholinophenyl) -2-dimethylamino-2- [4- (2-diethylaminoethyl) benzyl] -butan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino -2-benzyl-butan-1-one-trifluoroacetate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-dodecylbenzenesulfonate,
1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one-p-toluenesulfonate, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-butane-1 -One-camphorsulfonate, 1- (4-morpholinophenyl)-
2-diethylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-benzyl-butan-1-one, 1- (4-morpholino Phenyl) -2-butylmethylamino-2-benzyl-butan-1-one, 1- (4
-Morpholinophenyl) -2-butylmethylamino-2
-(4-isopropylbenzyl) -butan-1-one,
1- (4-morpholinophenyl) -2-dibutylamino-2-benzyl-butan-1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-benzyl-butan-1-one, -(3-chloro-4-morpholinophenyl) -2-dimethylamino-2-benzyl-butan-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2-dimethyl Amino-2-benzyl-butan-1-one, 1- (1,4-dimethyl-1,2,3,4-tetrahydroquinoxaline-
6-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (N-butylcarbazol-3-yl) -2-dimethylamino-2-benzyl-butane-1
-One, 1- (1,3-benzodioxol-5-yl) -2-dimethylamino-2-benzyl-butane-1
-One, 1- (2,3-dihydrobenzofuran-5-yl) -2-dimethylamino-2-benzyl-butane-1
-One, 1- (xanthen-2-yl) -2-dimethylamino-2-benzyl-butan-1-one, 1- (2,
3-dihydro-2,3-dimethylbenzothiazole-5
-Yl) -2-dimethylamino-2-benzyl-butan-1-one, 2- (2-dimethylamino-2-benzyl-butanoyl) -fluorenone, 2- (2-dimethylamino-2-benzyl-butanoyl) -Dibenzosuberone, 3,6-di (2-dimethylamino-2-benzyl-
(Butanoyl) -9-butyl-carbazole and the like.

Pentane classified into 5 carbon atoms in the basic skeleton
As 1-one, 1- (4-morpholinophenyl) -2
-Dimethylamino-2-allyl-pentan-1-one,
1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-pentan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (2-isopropylbenzyl) -pentane-1 -ON, 1-(4
-Morpholinophenyl) -2-butylmethylamino-2
-(4-isobutylbenzyl) -pentan-1-one,
1- (4-morpholinophenyl) -2-butylmethylamino-2- (4-butoxybenzyl) -pentane-1-
ON and the like.

Further, as penten-1-one, 1-phenyl-2-dimethylamino-2-methyl-4-penten-1-one, 1-phenyl-2-dimethylamino-2
-Ethyl-4-penten-1-one, 1-phenyl-2
-Dimethylamino-2-benzyl-4-pentene-1-
On, 1-phenyl-2-morpholino-2-methyl-4
-Penten-1-one, 1-phenyl-2-morpholino-2-benzyl-4-penten-1-one, 1,2-diphenyl-2-morpholino-4-penten-1-one,
1- (4-methylphenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-dodecylphenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1
-(4-methoxyphenyl) -2-dibutylamino-2
-Methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-piperidino-2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-
Oxazolidino-2-methyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-
2-ethyl-4-penten-1-one, 1- (4-methoxyphenyl) -2-morpholino-2-phenyl-4-
Penten-1-one, 1- (3,4-dimethoxyphenyl) -2-morpholino-2-ethyl-4-penten-1
-One, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-methyl-4-pentene-1
-One, 1- [4- (2-methoxyethoxy) phenyl] -2-morpholino-2-ethyl-4-pentene-1
-One, 1- [4- (2-hydroxyethoxy) phenyl] -2-morpholino-2-ethyl-4-pentene-1
-One, 1- (4-isopropyloxyphenyl) -2
-Dimethylamino-2-benzyl-4-pentene-1-
On, 1- (4-butyloxyphenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- [4
-(2-allyloxyethoxy) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1-
[4- (2-allyloxyethoxy) phenyl] -2-
Morpholino-2-ethyl-4-penten-1-one, 1
-(4-trimethylsilyloxyphenyl) -2-morpholino-2-methyl-4-penten-1-one, 1-
(4-fluorophenyl) -2-dimethylamino-2-
Methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-fluorophenyl) -2
-Dimethylamino-2-benzyl-4-pentene-1-
On, 1- (4-fluorophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-4-
Penten-1-one, 1- (4-fluorophenyl)-
2-morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-fluorophenyl) -2-morpholino-2-ethyl-5-methyl-4-penten-1
-One, 1- (4-fluorophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1-
(3,4-dichlorophenyl) -2-dimethylamino-
2-ethyl-4-penten-1-one, 1- (3,5-
Dichloro-4-methoxyphenyl) -2-morpholino-
2-methyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-bromophenyl) -2-morpholino- 2-ethyl-4-penten-1-one, 1-
(4-bromophenyl) -2-morpholino-2-t-butyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-dimethylamino-2-methyl-4-penten-1-one , 1- (4-methylthiophenyl)-
2-dimethylamino-2-ethyl-4-pentene-1-
On, 1- (4-methylthiophenyl) -2-dimethylamino-2-phenyl-4-penten-1-one, 1-
(4-methylthiophenyl) -2-dimethylamino-2
-Benzyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-piperidino-2-ethyl-4-
Penten-1-one, 1- (4-methylthiophenyl)
-2-morpholino-2-methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-ethyl-4
-Methyl-4-penten-1-one, 1- (4-methylthiophenyl) -2-morpholino-2-phenyl-4-
Penten-1-one, 1- (4-methylthiophenyl)
-2-morpholino-2-benzyl-4-pentene-1-
On, 1- (4-ethylthiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4-
(Isopropylthiophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-allylthiophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- [ 4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-ethyl -4-
Penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-propyl-
4-penten-1-one, 1- [4- (2-hydroxyethylthio) phenyl] -2-morpholino-2-t-butyl-4-penten-1-one, 1- [4- (2-methoxy Carbonylethylthio) phenyl] -2-morpholino-2-methyl-4-penten-1-one, 1- (4-
Methylsulfonylphenyl) -2-dimethylamino-2
-Ethyl-4-penten-1-one, 1- (4-butylsulfinylphenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- [4- (4-methylphenylthio) Phenyl] -2-morpholino-2-ethyl-4-penten-1-one, 1- [4- (4-methylphenylsulfonyl) phenyl] -2-morpholino-
2-ethyl-4-methyl-4-penten-1-one, 1
-(4-chlorophenylthiophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1-
(4-dimethylaminophenyl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-ethyl-4-penten-1- On, 1- (4-dimethylaminophenyl) -2-dimethylamino-2-benzyl-
4-penten-1-one, 1- (4-dimethylaminophenyl) -2-methylphenylamino-2-ethyl-4
-Penten-1-one, 1- (4-dimethylaminophenyl) -2- (pyrrolidin-1-yl) -2-methyl-
4-penten-1-one, 1- (4-dimethylaminophenyl) -2-morpholino-2-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2
-Morpholino-2-ethyl-4-methyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2
-Morpholino-2-benzyl-4-penten-1-one, 1- (4-dimethylaminophenyl) -2- (2,
6-dimethylmorpholin-4yl) -2-ethyl-4-
Penten-1-one, 1- (4-diethylaminophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- [4-bis (2-methoxyethyl)
Aminophenyl] -2-morpholino-2-methyl-4-
Penten-1-one, 1- (4-butylaminophenyl) -2-dibutylamino-2-methyl-4-penten-1-one, 1- (4-butylaminophenyl) -2-
Morpholino-2-methyl-4-penten-1-one, 1
-(4-dibutylaminophenyl) -2-morpholino-
2-methyl-4-penten-1-one, 1- (4-diallylaminophenyl) -2-morpholino-2-methyl-
4-penten-1-one, 1- [4- (pyrrolidine-1
-Yl) phenyl] -2-morpholino-2-methyl-4
-Penten-1-one, 1- (4-piperidinophenyl) -2-piperidino-2-methyl-4-penten-1
-One, 1- [4- (piperazin-1-yl) phenyl] -2-dimethylamino-2-ethyl-4-penten-1-one, 1- [4- (4-methylpiperazin-1-
Yl) phenyl] -2-morpholino-2-methyl-4-
Penten-1-one, 1- [4- (N-methylpiperazin-1-yl) phenyl] -2- (N-methylpiperazin-1-yl) -2-methyl-4-penten-1-one, -(4-morpholinophenyl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (4
-Morpholinophenyl) -2-dimethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-isopropyl-
4-penten-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-
Diethylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino-2-ethyl-4-penten-1
-One, 1- (4-morpholinophenyl) -2-butylmethylamino-2-methyl-4-penten-1-one,
1- (4-morpholinophenyl) -2-allylmethylamino-2-ethyl-4-penten-1-one, 1- (4
-Morpholinophenyl) -2-diallylamino-2-ethyl-4-penten-1-one, 1- (4-morpholinophenyl) -2-benzylmethylamino-2-ethyl-
4-penten-1-one, 1- (4-morpholinophenyl) -2- (piperazin-1-yl) -2-ethyl-4
-Penten-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-methyl-4-penten-1
-One, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (4
-Morpholinophenyl) -2-morpholino-2-ethyl-4-penten-1-one-dodecylbenzenesulfonate, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-methyl-4-pentene- 1-one, 1- (4-morpholinophenyl) -2-morpholino-2-benzyl-4-penten-1-one, 1- [4-
(2,6-dimethylmorpholin-4-yl) phenyl]
-2-morpholin-2-methyl-4-penten-1-one, 1- [4- (2,6-dimethylmorpholin-4-yl) phenyl] -2- (2,6-dimethylmorpholin-
4-yl) -2-ethyl-4-penten-1-one, 1
-(N-butylindoline-5-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (1,
4-dibutyl-1,2,3,4-tetrahydroquinoxalin-6-yl) -2-morpholino-2-ethyl-4-
Penten-1-one, 1- (N-butylcarbazole-
3-yl) -2-morpholino-2-ethyl-4-penten-1-one, 1- (5,10-dibutyl-5,10-
Dihydrophenazin-6-yl) -2-dimethylamino-2-methyl-4-penten-1-one, 1- (1,3
-Benzodioxol-5-yl) -2-morpholino-
2-methyl-4-penten-1-one, 1- (benzofuran-3-yl) -2-morpholino-2-ethyl-4-
Penten-1-one, 1- (benzofuran-6-yl)
-2-morpholino-2-ethyl-4-penten-1-one, 1- (2,3-dihydrobenzofuran-5-yl)
-2-morpholino-2-methyl-4-penten-1-one, 1- (N-methylphenothiazin-2-yl) -2
-Dimethylamino-2-allyl-4-penten-1-one, 3,6-di (2-morpholino-2-methyl-4-pentenoyl) -carbazole, 2- (2-dimethylamino-2-allyl-4 -Pentenoyl) -acridanone,
2- (2-morpholino-2-methyl-4-pentenoyl) -xanthone, 2- (4-morpholinobenzoyl)
-2-ethyl-N-methyl-1,2,3,6-tetrahydropyridine and the like.

Hexane classified as having 6 carbon atoms in the basic skeleton
As 1-one, 1- (4-methylthiophenyl) -2
-Morpholino-2-allyl-hexane-1-one, 1-
(4-morpholinophenyl) -2-dimethylamino-2
-Benzyl-hexane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-
4,5,5-trimethyl-hexane-1-one, 1-
(4-morpholinophenyl) -2-butylmethylamino-2- (4-butylbenzyl) -hexane-1-one,
1- (4-morpholinophenyl) -2-dioctylamino-2- (4-methylbenzyl) -hexane-1-one and the like.

Further, as hexen-1-one, 1-
(4-methylthiophenyl) -2-morpholino-2-ethyl-4-methyl-4-hexen-1-one, 1- (4
-Dimethylaminophenyl) -2-dimethylamino-
2,4,5-trimethyl-4-hexen-1-one, 1
-(4-dimethylaminophenyl) -2-morpholino-
2-ethyl-4-hexen-1-one, 1- (4-morpholinophenyl) -2-morpholino-2-ethyl-4-
Hexen-1-one and the like.

Heptane classified into C7 of the basic skeleton
As 1-one, 1- (4-dimethylaminophenyl)
2-dimethylamino-2- [4- (2-methoxy) benzyl] -heptan-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2-benzyl-heptan-1-one and the like. No.

Further, as hepta-1,6-diene, 4
-Benzoyl-4-dimethylamino-hepta-1,6-
Diene, 4- (4-methoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-methoxybenzoyl) -4-morpholino-hepta-1,6-diene, 4- (3, 4-dimethoxybenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-phenoxybenzoyl) -4-dimethylamino-hepta-
1,6-diene, 4- (4-fluorobenzoyl) -4
-Dimethylamino-hepta-1,6-diene, 4- (4
-Fluorobenzoyl) -4-morpholino-hepta-
1,6-diene, 4- (4-methylthiobenzoyl)-
4-dimethylamino-hepta-1,6-diene, 4-
(4-methylthiobenzoyl) -4-morpholino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl) -4-dimethylamino-hepta-1,6-diene, 4- (4-dimethylaminobenzoyl ) -4-morpholino-hepta-1,6-diene, 4- (4-morpholinobenzoyl) -4-dimethylamino-hepta-1,6
-Diene, 4- (4-morpholinobenzoyl) -4-morpholino-hepta-1,6-diene and the like.

Octane classified into carbon number 8 of the basic skeleton
As 1-one, 1- (4-morpholinophenyl) -2
-Dimethylamino-2-benzyl-octane-1-one, 1- (4-morpholinophenyl) -2-dimethylamino-2- (4-dodecylbenzyl) -octane-1-
ON and the like.

The photopolymerizable composition of the present invention comprises, as essential components, the ethylenically unsaturated compound of component (A), the infrared absorbing dye of component (B), and the α-aminoacetophenone derivative of component (C). The content ratio of the components (B) and (C) to the component (A) is 100% for the component (A).
Component (B) is preferably 1 to 30 parts by weight, component (C) is preferably 1 to 40 parts by weight, and component (B) is 2 to 30 parts by weight.
Particularly preferred is 25 parts by weight and 2 to 35 parts by weight of the component (C). When the content ratio of each of the component (B) and the component (C) is less than the above range, the sensitivity tends to be insufficient as the photopolymerizable composition of the present invention. In such a case, problems such as loss of uniformity as a composition layer tend to occur.

In the photopolymerizable composition of the present invention, the ratio of the component (B) to the component (C) is as follows:
The weight ratio of the component (C) is preferably in the range of 1:20 to 10: 1, and more preferably in the range of 1: 8 to 4: 1.

The photopolymerizable composition of the present invention may further comprise, in addition to the above components, an alkali-soluble resin (D) as a binder component in an amount of 10 to 5 parts by weight based on 100 parts by weight of the component (A).
It is preferably contained in an amount of 00 parts by weight, more preferably 20 to 200 parts by weight.

In the present invention, as the alkali-soluble resin, a carboxyl group-containing polymer is preferable. Specifically, for example, (meth) acrylic acid, 2-succinoloyloxyethyl methacrylate, methacrylic acid 2 A homopolymer of an unsaturated carboxylic acid such as maleinoloyloxyethyl, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and , These unsaturated carboxylic acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) Acrylate, benzyl (meth) a Relate, N, N- dimethylaminoethyl (meth) acrylate, N- (meth) acryloyl morpholine, (meth) acrylonitrile, (meth) acrylamide, N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide,
Copolymers with unsaturated compounds such as N, N-dimethylaminoethyl (meth) acrylamide, glycidyl crotonate ether, allyl glycidyl ether, styrene, α-methylstyrene, vinyl acetate, etc .; The combined acid value is 10-250KOH
mg / g and the weight average molecular weight are preferably 0.5 to 500,000.

Further, as the carboxyl group-containing polymer, a polymer obtained by hydrolyzing or half-esterifying an acid anhydride unit of an acid anhydride-containing polymer is preferable.
For example, a maleic anhydride unit of a copolymer of maleic anhydride and styrene, α-methylstyrene, or the like is hydrolyzed with water, or methanol, ethanol, propanol, butanol, hydroxyethyl (meth) acrylate, or the like. One obtained by half-esterification with a monohydric alcohol is exemplified.

Further, as a carboxyl group-containing polymer,
Those obtained by modifying an epoxy resin with a monocarboxylic acid and an acid anhydride are also preferable. Specifically, for example, a novolak epoxy acrylate resin, a bisphenol epoxy resin, or the like can be obtained by adding (meth) acrylic acid, 2-succinoloy methacrylate, or the like. Unsaturated monomers such as ruoxyethyl, 2-maleinoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, and itaconic acid Carboxylic acid, or acetic acid, propionic acid, after adding a saturated monocarboxylic acid such as stearic acid, modified with an acid anhydride such as maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, phthalic anhydride Is mentioned.

Further, as the carboxyl group-containing polymer, those having an ethylenically unsaturated bond in the side chain are also suitable. Specifically, for example, allyl glycidyl ether, glycidyl ( (Meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate Or an unsaturated compound having an alicyclic epoxy group such as an aliphatic epoxy group-containing unsaturated compound such as 3,4-epoxycyclohexylmethyl (meth) acrylate or the like. Le%, preferably 30 to 70 mol%
A reaction product obtained by reacting to a degree, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate,
Compounds having two or more types of unsaturated groups such as methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl ( A compound having two or more unsaturated groups such as (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide, and (meth)
An unsaturated carboxylic acid such as acrylic acid or an unsaturated carboxylic acid ester is used in an amount of 10 to 90 mol%, preferably 30 to 90 mol%, of the total of the former compound having an unsaturated group.
A reaction product obtained by copolymerizing so as to be about 80 mol% is exemplified.

Further, as the alkali-soluble resin suitable in the present invention, for example, phenol, o-cresol, m
-Cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m
-Ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol,
At least one phenol such as 1,2,4-benzenetriol and phloroglucinol is converted to an aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, furfural and the like under an acidic catalyst, or , Acetone, methyl ethyl ketone, a novolak resin polycondensed with at least one of ketones such as methyl isobutyl ketone, and polycondensation was carried out in the same manner except that an alkali catalyst was used in place of the acid catalyst in the polycondensation of the novolak resin. Resole resin and, for example, o-
Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene,
Examples thereof include polyvinyl phenol resins obtained by polymerizing hydroxy styrenes alone or two or more kinds such as 2- (p-hydroxyphenyl) propylene in the presence of a radical polymerization initiator or a cationic polymerization initiator. It is preferable that the average molecular weight is 0.1000 to 50,000.

The photopolymerizable composition of the present invention may contain, if necessary, a coating improver such as a nonionic, anionic, cationic or fluorine-based surfactant, an antifoaming agent, a visible image. Additives such as a property imparting agent, a colorant, an adhesion improver, a developability improver, an ultraviolet absorber, and a polymerization stabilizer may be added.

The use form of the photopolymerizable composition of the present invention as a light-sensitive material may be determined, for example, by applying it to a support without a solvent or by diluting it with a suitable solvent, and then drying the coating. A form, or a form in which an overcoat layer for blocking oxygen is further provided thereon, a form in which droplets are dispersed in a heterogeneous medium and applied in multiple layers as a plurality of types of photosensitive materials, and a support in which microcapsules are included Although the form and the like coated on the photopolymerizable composition of the present invention can be adopted, the composition is coated on a support surface as a solution in which the composition is dissolved in an appropriate solvent,
It is preferably used as a photopolymerizable image forming material in which a layer of the photopolymerizable composition of the present invention is formed on the surface of a support by heating and drying.

Here, the solvent is not particularly limited as long as it has sufficient solubility in the components used and gives good coating properties.
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvents such as methyl 3-methoxypropionate, heptanol Hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone, ketone solvents such as methyl amyl ketone,
Highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, or a mixed solvent thereof, and further a mixture thereof with an aromatic hydrocarbon may be used. The usage ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the total amount of the photopolymerizable composition.

As a method of coating, a conventionally known method is used.
Methods, such as spin coating, wire bar coating, dip coating
Cloth, air knife coating, roll coating, blade coating,
And curtain coating can be used. Application amount is application
The dry film thickness varies from 0.1 to 100 g /
m^TwoIs preferably in the range of 0.5 to 70 g / m ^Two
It is more preferable to be within the range. The drying temperature at that time
For example, about 30 to 150 ° C., preferably 4
The drying time is about 0 to 110 ° C., for example, 5 seconds to
About 60 minutes, preferably about 10 seconds to 30 minutes
It is.

As the support, aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Paper, paper coated with resin, paper bonded with metal foil such as aluminum, plastic film, plastic film subjected to hydrophilic treatment, epoxy resin, polyimide resin, copper-clad laminate such as glass cloth base epoxy resin, and glass Plates and the like are included. Among them, an aluminum plate is preferable.

Prior to the formation of the photopolymerizable composition layer on the surface of the aluminum plate support, usually, a degreasing treatment, a roughening treatment (graining treatment), an anodic oxidation treatment, a water washing treatment and the like are performed. The surface-treated one is used, and its thickness is usually 0.01 to 10 mm, preferably 0.1 to 10 mm.
About 0.5 to 1 mm, and the surface roughness is JIS
Average roughness R _a as defined in B0601, usually, 0.3
１．０1.0 μm, preferably about 0.4-0.8 μm.

Light sources for imagewise exposing the photopolymerizable composition of the present invention include carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, HeNe laser, argon ion laser, YAG laser, A laser light source such as a HeCd laser, a semiconductor laser, and a ruby laser may be used. In particular, a light source that generates an infrared laser beam having a wavelength of 700 nm or more is preferable. Particularly, a semiconductor laser or a YAG laser having a small size and a long life is preferable.

The photopolymerizable composition of the present invention has a high sensitivity to such infrared laser light,
mj / cm ² or less, preferably 10 to 400 mj / cm
Exposure is performed as ² , and after exposure, development is performed with a developer to form a negative image.

Examples of the developer used for developing the photosensitive material obtained by imagewise exposing the photopolymerizable composition of the present invention include sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate, and water. Sodium oxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium diphosphate, sodium tertiary phosphate, ammonium diphosphate, ammonium tertiary phosphate, sodium borate, potassium borate, ammonium borate, etc. An inorganic alkali salt, or
Organic amine compounds such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and diisopropanolamine; An alkaline developer comprising an aqueous solution of about 0.1 to 10% by weight is used. Incidentally, a nonionic, anionic, cationic or amphoteric surfactant or an organic solvent such as alcohol may be added to the developer as required.

The development is usually carried out by immersion development, spray development, brush development, ultrasonic development, or the like.
To about 60 ° C, more preferably about 15 to 45 ° C.

[0060]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support, and the surface of the aluminum plate support was treated as an ethylenically unsaturated compound as the component (A). 50 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of the phthalocyanine dye of R-11 described in the specific examples as the infrared absorbing dye of the component (B), and 1- as the α-aminoacetophenone derivative of the component (C). 10 parts by weight of (4-morpholinophenyl) -2-dimethylamino-2-benzyl-1-butan-1-one (“IRG-369” manufactured by Ciba-Geigy), and
As the alkali-soluble resin (D), a styrene / acrylic acid copolymer (weight average molecular weight 5000, acid value 20)
Reaction product obtained by reacting 3,4-epoxycyclohexylmethyl acrylate with 0) (oxidation 80, 50 mol% of carboxyl groups of acrylic acid component react) 50
Parts by weight of a coating solution prepared by stirring at room temperature with 1500 parts by weight of cyclohexanone at room temperature, using a wire bar, applying the coating solution, and drying at 70 ° C. for 1 minute to form a 1 μm-thick photopolymerizable composition layer. Further, a 10% by weight aqueous solution of polyvinyl alcohol was applied thereon and dried to form an overcoat layer having a thickness of 1 μm, thereby producing a photopolymerizable image forming material.

The obtained photopolymerizable image-forming material was treated with a diameter of 10
cm on a stainless steel rotating drum so that the photopolymerizable composition layer is on the outside, and then the drum is rotated at 5 rpm and 5 rpm.
While rotating at four rotation speeds of 0 rpm, 100 rpm, and 200 rpm, a wavelength of 830 nm and an output of 40
mW semiconductor laser ("HL8325" manufactured by Hitachi, Ltd.
C)), and was exposed by scanning with a beam spot condensed to 30 μm, and then developed by immersion in a 1% by weight aqueous solution of sodium silicate at 25 ° C. for 60 seconds to form a negative image of a scanning line.

At this time, the sensitivity is evaluated based on the maximum number of rotations of the drum on which the line image is formed. Further, the edge portion of the image at the maximum number of rotations is observed with a microscope of 100 times, and the edge portion is sharply formed. Observing the resolution as “good” for those that have been done and “bad” for those that are not, and also observing the non-image part (non-exposed part) at the maximum rotation speed in the same way. Developability was evaluated as "good" for no one and "poor" for some stains.
The results are shown in Table 1.

Example 2 The infrared absorbing dye of the component (B) was replaced by R
Example 1 was repeated except that the phthalocyanine dye of -12 was used.
A photopolymerizable image-forming material was prepared in the same manner as described above, and the sensitivity, resolution, and developability were evaluated in the same manner. The results are shown in Table 1.

Example 3 The ethylenically unsaturated compound as the component (A) was replaced with a urethane acrylate compound ("UA-306H" manufactured by Kyoeisha Co., Ltd.) which is a reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate. In the same manner as in Example 2, a photopolymerizable image-forming material was produced, and the sensitivity, resolution, and developability were evaluated in the same manner. The results are shown in Table 1.

Example 4 Example 2 was repeated except that the ethylenically unsaturated compound (A) was replaced by 2,2-bis [4-acryloyloxydi (ethyleneoxy) phenyl] propane (manufactured by Kyoeisha). Similarly, to produce a photopolymerizable image forming material, in the same manner,
The sensitivity, resolution, and developability were evaluated, and the results are shown in Table 1.

COMPARATIVE EXAMPLE 1 Except that the components (B) and (C) were replaced with a radical-generating dye represented by the following formula, which is a complex of a cyanine dye cation and an organic boron anion: A photopolymerizable image-forming material was prepared in the same manner as in Example 2, and the sensitivity,
The resolution and the developability were evaluated, and the results are shown in Table 1.

[0068]

Embedded image

Comparative Example 2 A photopolymerizable image forming material was prepared in the same manner as in Example 2 except that only the component (B) was replaced with the same radical-generating dye as used in Comparative Example 1. Sensitivity, resolution,
And the developability were evaluated, and the results are shown in Table 1.

[0070]

[Table 1]

[0071]

According to the present invention, a photopolymerizable composition and a photopolymer composition which are highly sensitive to light in the infrared region, particularly to infrared laser light, and which can be directly drawn by a semiconductor laser, a YAG laser or the like. A polymerizable image forming material and a negative image forming method can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 502 G03F 7/027 502 7/032 7/032 7/32 7/32 F-term (reference) 2H025 AA01 AB03 AB09 AC08 AD01 BC13 BC31 CA04 CA27 CB42 CC11 FA03 FA10 FA17 2H048 BA45 BA47 BA48 BB42 2H096 AA06 AA23 BA05 EA04 GA08 4J011 PA65 PA69 PA70 PA85 PA86 PB40 QA13 QA14 QA17 QA18 QA18 QA18 QA18 QA18 QA18

Claims (7)

[Claims] 1. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) Ethylenically unsaturated compound (B) Infrared absorbing dye that does not generate active radicals by itself (C) α-Aminoacetophenone derivative 2. The photopolymerizable composition according to claim 1, wherein the infrared absorbing dye as the component (B) is nonionic. 3. The photopolymerizable composition according to claim 2, wherein the nonionic infrared absorbing dye is a phthalocyanine compound. 4. The photopolymerizable composition according to claim 1, wherein the (C) component α-aminoacetophenone derivative is represented by the following general formula (I). Embedded image [In the formula (I), R ¹ represents an alkyl group which may have a substituent, an allyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent. R ² represents an alkyl group optionally having a substituent, an allyl group optionally having a substituent, or an optionally substituted benzyl group. Represents a benzyl group,
R ³ and R ⁴ are each independently an alkyl group which may have a substituent, an allyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent And R ³ and R ⁴ are linked to each other, or R ³ or R ⁴ and R ¹ or R ²
And may be connected to each other to form a cyclic structure,
The benzene ring may have a substituent. ] 5. The photopolymerizable composition according to claim 1, further comprising an alkali-soluble resin (D). 6. A photopolymerizable image-forming material comprising a support and a layer comprising the photopolymerizable composition according to claim 1 formed on a surface of the support. 7. A negative image, comprising subjecting the photopolymerizable image forming material according to claim 6 to image exposure with an infrared laser beam at an exposure of 500 mj / cm ² or less, and then developing with an aqueous alkali solution. Forming method.