JP2002214784A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity particularly to visible light in a short wavelength range and preventing the lowering of color purity when a colored relief image is formed as a photopolymerizable composition containing a coumarin compound as a sensitizing dye. SOLUTION: The photopolymerizable composition contains (A) an ethylenically unsaturated compound, (B) a sensitizing dye comprising a coumarin compound of formula (I) (where R1 and R2 are each alkyl which may have a substituent and R3 is alkyl which may have a substituent, cycloalkyl which may have a substituent or aryl which may have a substituent) and (C) a photopolymerization initiator.

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 for a liquid crystal display or a plasma display, a photoresist for an integrated circuit of a semiconductor element, a copper etching resist for a wiring board or a gravure plate. For use in the preparation, relates to a photopolymerizable composition showing high sensitivity to a light source mainly in the visible region, more specifically, in a photopolymerizable composition containing a coumarin compound as a sensitizing dye, particularly, a short wavelength The present invention relates to a photopolymerizable composition which has high sensitivity to visible light sources in the region and has no decrease in color purity when a colored relief image is formed.

[0002]

2. Description of the Related Art Heretofore, as a method for forming an image by exposing a photopolymerizable composition to light, a method comprising forming an ethylenically unsaturated compound, a sensitizing dye, and a photopolymerization initiator, or further comprising a polymer binder, a colorant, or the like. Forming a layer of the polymerizable composition on the support surface,
Image exposure to polymerize the ethylenically unsaturated compound in the exposed area,
A method of forming a cured relief image by dissolving and removing an unexposed portion after curing is widely used, and various types of ethylenic non-aqueous materials are used for the purpose of improving the sensitivity and the like of the photopolymerizable composition. Many proposals have been made regarding saturated compounds, sensitizing dyes, photopolymerization initiators, etc. Among them, coumarin-based compounds have long been known as sensitizing dyes, and particularly, ketones at the 3-position of coumarin are known. A ketocoumarin-based compound having a structure has been used practically since it has good properties and its synthesis is easy.Besides, as a combination of a ketocoumarin-based compound and a polymerization initiator, for example, hexaarylbi Compositions using an imidazole compound as a polymerization initiator (for example, Japanese Patent Publication No. 5-8824)
See No. 4 publication. ) And compositions using a titanocene compound as a polymerization initiator (see, for example, JP-A-63-221110).

On the other hand, the demands for photopolymerizable photosensitive materials in recent years have been diversified, for example, a light source in the visible region,
For example, while it is required to exhibit high sensitivity to g-line, conventionally known photopolymerizable compositions using a coumarin-based compound including a ketocoumarin-based compound as a sensitizing dye do not necessarily exhibit high sensitivity. In addition, for example, in the field of forming a color resist image such as a color filter or a color proof, it has been pointed out that problems such as unintended coloring in a visible region and reduction in color purity have been pointed out, and improvement thereof is required. .

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and accordingly, the present invention relates to a photopolymerizable composition containing a coumarin compound as a sensitizing dye. In particular, it is an object of the present invention to provide a photopolymerizable composition which exhibits high sensitivity to a visible light source in a short wavelength region and has no decrease in color purity when a colored relief image is formed.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a photopolymerizable composition containing a coumarin compound containing a specific structural unit can achieve the above object. Find out what completed the present invention,
That is, the gist of the present invention is a photopolymerizable composition containing the following components (A), (B), and (C).

(A) Ethylenically unsaturated compound (B) Sensitizing dye comprising coumarin compound represented by the following general formula (I)

[0007]

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[0008] wherein (I), R ¹ and R ² each independently represents an optionally substituted alkyl group, R ³
Represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. ]

(C) Photopolymerization initiator

[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 at least one radically polymerizable ethylenically unsaturated bond in a molecule which undergoes addition polymerization by the action of a photopolymerization initiation system containing a photopolymerization initiator as a component, and in some cases, crosslinks and cures.

As the ethylenically unsaturated compound in the present invention, a compound having one ethylenically unsaturated bond in the molecule, specifically, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, Unsaturated carboxylic acids such as itaconic acid and citraconic acid, and alkyl esters thereof, (meth) acrylonitrile, (meth) acrylamide, styrene and the like may be used. It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, for example, from the viewpoint that the difference in solubility in the developing solution can be enlarged.
It is particularly preferable that the unsaturated bond is an acrylate compound derived from a (meth) acryloyloxy group.
Here, “(meth) acryl” means acryl or methacryl, and the same applies hereinafter.

The compound having two or more ethylenically unsaturated bonds in a molecule is typically an ester of an unsaturated carboxylic acid with a polyhydroxy compound, or a compound of a hydroxy (meth) acrylate compound with a polyisocyanate compound. Examples include urethane (meth) acrylates, epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, and (meth) acryloyloxy group-containing phosphates.

Specific examples of the esters include unsaturated carboxylic acids as described above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, trimethylene glycol and tetramethylene glycol. Methylene glycol, neopentyl glycol, hexamethylene glycol, nonamethylene glycol, trimethylolethane, tetramethylolethane,
Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, reactants with aliphatic polyhydroxy compounds such as triethanolamine, 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, tripropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) ) Acrylate, nonamethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethylene oxide added tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycer Lumpur propylene oxide addition 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 tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth)
Acrylates and the like, and similar crotonates, isocrotonates, maleates, itaconates, citraconates and the like can be mentioned.

Further, as the esters, a reaction product of the above unsaturated carboxylic acid with an aromatic polyhydroxy compound such as hydroquinone, resorcinol, pyrogallol, bisphenol F and bisphenol A, specifically, for example, hydroquinone Di (meth) acrylate, resorcinol di (meth) acrylate, pyrogallol tri (meth)
Acrylates and the like, and an unsaturated carboxylic acid as described above,
Reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, specifically, for example, di (meth) acrylate, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate A reaction product of an unsaturated carboxylic acid, a polycarboxylic acid and a polyhydroxy compound, specifically, for example, a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, (meth) acrylic acid And condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, and condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin.

As the urethane (meth) acrylates, specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate , A hydroxy (meth) acrylate compound such as tetramethylolethane tri (meth) acrylate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine methyl ester triisocyanate, dimer acid diisocyanate, , 6,11-Undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Aliphatic polyisocyanates, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, alicyclic polyisocyanates such as bicycloheptane triisocyanate, p- phenylene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, tris (isocyanate phenyl methane) And polyisocyanate compounds such as aromatic polyisocyanates such as tris (isocyanatephenyl) thiophosphate and heterocyclic polyisocyanates such as isocyanurate.

The epoxy (meth) acrylates include, for example, (meth) acrylic acid,
Or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, Aliphatic poly such as (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Epoxy compounds, phenol novolak polyepoxy compounds, brominated phenol novolak polyepoxy compounds, (o-, m-,
p-) Aromatic polyepoxy compounds such as cresol novolak polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. And a reaction product thereof with a polyepoxy compound such as a heterocyclic polyepoxy compound.

Examples of the (meth) acryloyloxy group-containing phosphates include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate,
(Meth) acryloyloxyethylene glycol phosphate and the like.

Other ethylenically unsaturated compounds other than those described above include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, and vinyl groups such as divinyl phthalate. And the like. The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

(B) Constituting the Photopolymerizable Composition of the Invention
The component sensitizing dye efficiently absorbs particularly light in the visible region having a wavelength of 450 to 600 nm, and transmits the photoexcitation energy to the photopolymerization initiator of the component (C) described below to decompose the photopolymerization initiator. And the component (A) has a sensitizing function of generating an active radical which induces the polymerization of the ethylenically unsaturated compound. In the present invention, the coumarin compound represented by the following general formula (I) Is essential. If the photopolymerizable composition of the present invention does not contain a coumarin compound represented by the general formula (I) as a sensitizing dye, the object of the present invention cannot be achieved.

[0020]

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[0021] wherein (I), R ¹ and R ² each independently represents an optionally substituted alkyl group, R ³
Represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent. ]

In the formula (I), the alkyl group of R ¹ and R ² preferably has 1 to 12 carbon atoms. The substituent of the alkyl group is, for example, 1 to 8 carbon atoms. Examples include an alkoxy group, a phenyl group, a phenoxy group, and a halogen atom.

The alkyl group of R ³ also has 1 to 12 carbon atoms.
It is preferable that the cycloalkyl group has 5 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. In addition, examples of the substituent of the alkyl group, cycloalkyl group, and aryl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenoxy group, a hydroxyl group, and a halogen atom.

Specific examples of the coumarin compound represented by the above general formula (I) are shown below by listing each group of R ¹ , R ² and R ^{3 in} the following Table 1.

[0025]

[Table 1]

These coumarin compounds can be easily synthesized by a conventional method, for example, by a condensation reaction between 4-dialkylaminosalicylic aldehyde and malonic ester.

In the present invention, the sensitizing dye of the component (B) is disclosed, for example, in US Pat. No. 3,479,185, in addition to the coumarin compound represented by the general formula (I). Triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green; photoreducing dyes such as erythrosine and eosin Y;
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in U.S. Pat. Nos. 3,549,367 and 3,652,275;
Β-diketones disclosed in US Pat. No. 4,790,464, indanones disclosed in US Pat. No. 4,162,162, JP-A-6-301208, JP-A-8-12925.
No. 8, JP-A-8-129259, JP-A-8-1466
Coumarin-based pigments disclosed in JP-A Nos. 05-111605 and 8-221605, ketocoumarin-based pigments disclosed in JP-A-52-112681, and JP-A-59-564.
Aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in U.S. Pat.
No. 10, aminophenyl heterocycles disclosed in U.S. Pat. No. 4,966,830; julolidine heterocycles disclosed in U.S. Pat. No. 4,966,830;
Compounds such as pyromethene pigments disclosed in JP-A-5885 and JP-A-10-144242 may be used in combination.

(C) Constituting the Photopolymerizable Composition of the Invention
The photopolymerization initiator of the component is a radical generator that generates an active radical when irradiated with light in the co-presence of the component (B) with the sensitizing dye and the like. Imidazole derivatives, titanocene derivatives, halomethylated s-triazine derivatives, halomethylated 1,
3,4-oxadiazole derivatives, diaryliodonium salts, carbonyl compounds, organic peroxides, and the like. In the present invention, hexaarylbiimidazole derivatives, titanocene derivatives, and carbonyl compounds Among them, benzophenone derivatives containing a dialkylamino group are preferred.

Here, as the hexaarylbiimidazole derivatives, specifically, for example, 2,2'-
Bis (o-methoxyphenyl) -4,4 ', 5,5'-
Tetraphenylbiimidazole, 2,2'-bis (p-
(Methoxyphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-fluorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5'-tetra (m, m-dimethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl)-
4,4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-fluorophenyl) ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-
Dibromophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-
Tetra (o, p-dichlorophenyl) biimidazole,
2,2′-bis (o-bromophenyl) -4,4 ′,
5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl)-
4,4 ′, 5,5′-tetra (p-iodophenyl) biimidazole, 2,2′-bis (o-bromophenyl)
-4,4 ', 5,5'-tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-
(Chlorophenyl) -4,4 ', 5,5'-tetra (p-
Chloronaphthyl) biimidazole and the like.

Examples of the titanocene derivatives include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-difluorophenyl). ), Dicyclopentadienyltitanium bis (2,6-difluorophenyl),
Dicyclopentadienyl titanium bis (2,4,6-
Trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2
3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl) ,
Di (methylcyclopentadienyl) titanium bis (2,4,6-trifluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,5,6
-Tetrafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis [2,6-difluoro-3- (1 -Pyrrolyl)
Phenyl] and the like.

Specific examples of the halomethylated s-triazine derivatives include, for example, 2,4,6-tris (trichloromethyl) -s-triazine and 2-methyl-4,6-bis (trichloromethyl). Methyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl)- s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3, 4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-
Chlorophenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-ethoxynaphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6- Bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-
4,6-bis (tribromomethyl) -s-triazine,
2-methoxy-4,6-bis (tribromomethyl) -s
-Triazine and the like.

As the halomethylated 1,3,4-oxadiazole derivatives, specifically, for example, 2
-(P-methoxyphenyl) -5-trichloromethyl-
1,3,4-oxadiazole, 2- (p-methoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (o-benzofuryl) -5-trichloromethyl-1,3 , 4-oxadiazole, 2- [β-
(O-benzofuryl) vinyl] -5-trichloromethyl-1,3,4-oxadiazole and the like.

Specific examples of the diaryliodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, and diphenyliodonium hexafluoroarsenate.

Specific examples of the carbonyl compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, and 4-bromobenzophenone. , Michler's ketone, 4,4'-bis (dimethylamino) benzophenone, benzophenone derivatives such as 4,4'-bis (dimethylamino) benzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone , 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy-1-methylethyl- (p
-Isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-
2-methylphenylpropanone, 2-methyl- (4'-
Acetophenone derivatives such as (methylthio) phenyl) -2-morpholino-1-propanone, thioxanthone,
And thioxanthone derivatives such as 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Specific examples of the organic peroxides include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′,
4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t
-Octylperoxycarbonyl) benzophenone,
3,3 ′, 4,4′-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (aminoperoxycarbonyl) benzophenone, carbonylbis (t-butylperoxy dihydrogen 2-phthalate), carbonyl bis (t-hexylperoxy dihydrogen 2-phthalate) and the like.

The photopolymerizable composition of the present invention comprises, as essential components, the ethylenically unsaturated compound of the component (A), the sensitizing dye of the component (B), and the photopolymerization initiator of the component (C). However, further, a polymer binder having a function as a binder for the ethylenically unsaturated compound of the component (A), the sensitizing dye of the component (B), and the photopolymerization initiator of the component (C) It is preferable to contain the component (D).

As the polymer binder, a carboxyl group-containing vinyl resin is preferable.
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxy Ethyl (meth) acrylate,
Glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine,
(Meth) acrylonitrile, (meth) acrylamide,
N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and copolymers with vinyl compounds such as vinyl acetate are exemplified.

Further, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in a side chain are preferable. 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 And the like. An aliphatic epoxy group-containing unsaturated compound such as an epoxy compound or an alicyclic epoxy group-containing unsaturated compound such as 3,4-epoxycyclohexylmethyl (meth) acrylate 90 mol%, preferably 30 to 70
Mole% of the reaction product obtained, and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) ) Acrylates, compounds having two or more unsaturated groups such as N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate , A compound having two or more unsaturated groups such as 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide, and an unsaturated carboxylic acid such as (meth) acrylic acid or further unsaturated carboxylic acid Ester and the former compound having an unsaturated group 10 to 90 mol%, preferably and the like reaction product obtained by copolymerizing such that about 30 to 80 mol%.

The photopolymerizable composition of the present invention preferably further contains a hydrogen-donating compound (E) for the purpose of improving the photopolymerization initiation ability. Specifically, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4
Mercapto group-containing compounds such as (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol, trimethylolpropane tristhione Polyfunctional thiol compounds such as glyconate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoate, N
-Amino acids having an aromatic ring such as phenylglycine, or salts thereof such as ammonium or sodium salts, derivatives thereof such as esters, phenylalanine, or salts thereof such as ammonium or sodium salts, or derivatives thereof such as esters, or derivatives thereof And the like.

Further, the photopolymerizable composition of the present invention contains a coloring material (F) in the field of forming a color resist image such as a color filter or a color proof. Pigments can be used.

Examples of the dyes and pigments include phthalocyanine pigments, azo pigments, triphenylmethane pigments,
Organic pigments such as quinoline pigments and anthraquinone pigments,
Inorganic pigments such as carbon black, titanium oxide and chrome yellow, azo dyes, triphenylmethane dyes, cyanine dyes, anthraquinone dyes and the like can be mentioned. I. (Color Index) Name, C.I. I. Pigment Red 9 and 9
7, 122, 123, 149, 168, 17
7, 180, 192, 215, 216, 21
7, 220, 223, 224, 226, 22
7, 228, 240, 254, C.I. I. Pigment Green 7, 36, C.I. I. Pigment Blue 1
5, 15: 6, 22, 22, 60, 64, C.I. I. Pigment Black 7, C.I. I. Pigment Yellow 2
0, 24, 86, 93, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, C. I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Brown 23, 2
5, 26 and the like.

In the photopolymerizable composition of the present invention, the content ratio of the ethylenically unsaturated compound as the component (A), the sensitizing dye as the component (B), and the photopolymerization initiator as the component (C) is as follows. Preferably, based on 100 parts by weight of the component (A), the component (B) is 0.1 to 100 parts by weight, and the component (C) is 0.1 to 150 parts by weight. The component (B) is 0.5 to 50 parts by weight, and the component (C) is 0.5 to 70 parts by weight.

The content ratio of the polymer binder of the component (D), the hydrogen-donating compound of the component (E), and the coloring material of the component (F) is 100 parts by weight of the component (A). On the other hand, preferably, the component (D) is 10 to 500 parts by weight, the component (E) is 0.5 to 50 parts by weight, and the component (F) is
The component is 5 to 500 parts by weight, more preferably the component (D) is 20 to 300 parts by weight, and the component (E) is 1 part by weight.
To 30 parts by weight, and the component (F) is 10 to 300 parts by weight.

Further, the photopolymerizable composition of the present invention may contain various additives such as catechol, hydroquinone, pyrogallol, p-methoxyphenol, 2,
Thermal polymerization inhibitors such as 6-di-t-butyl-p-cresol and β-naphthol, dioctyl phthalate, didodecyl phthalate, dimethylene glycol phthalate, tricresyl phosphate, dioctyl adipate, triethylene glycol dicaprylate, triethylene glycol Various additives commonly used such as a plasticizer such as acetylglycerin, an adhesion improver such as a silane coupling agent, a coating improver, a developability improver, a sensitivity improver, and a sensitizer are further contained. You may.

The use form of the photopolymerizable composition of the present invention as a light-sensitive material is, for example, without a solvent or after being diluted with an appropriate solvent, applied to the surface of a support and dried. Although the photopolymerizable composition of the present invention may be in various forms such as a form, the composition is applied to a support surface as a solution in which the composition is dissolved in an appropriate solvent, and then heated and dried to form a support. It is suitable for use as a photopolymerizable image forming material having a layer of the photopolymerizable composition of the present invention formed on the surface.

Here, the solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives good coating properties. Examples of the solvent include methyl cellosolve,
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, furthermore, a solvent obtained by adding an aromatic hydrocarbon to these solvents, and the like. 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 the coating method, conventionally known methods, for example, spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The coating amount varies depending on the application, but is usually 0.3 to 7 μm as a dry film thickness.
m, preferably 0.5-5 μm, particularly preferably 1-3
μm range. The drying temperature at that time is, for example, about 60 to 170 ° C, preferably 70 to 150 ° C.
The drying time is about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes.

Incidentally, an oxygen barrier layer of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose or the like is usually provided on the photopolymerizable composition layer in order to prevent a polymerization inhibition effect by oxygen.

The support is made of aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Examples include paper, paper coated with resin, paper to which metal foil such as aluminum is adhered, plastic film, plastic film subjected to hydrophilic treatment, and glass plate.

In the present invention, the light source for imagewise exposing the photopolymerizable composition layer of the photopolymerizable image forming material includes a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, Further, a laser light source such as a helium neon laser, a helium cadmium laser, an argon ion laser, a YAG laser, and a semiconductor laser is used.

Examples of the developer used for developing the photoreceptor obtained by imagewise exposing the photopolymerizable image forming material of the present invention include:
Sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Inorganic alkali salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, sodium borate, potassium borate, ammonium borate, monomethylamine, dimethylamine, Trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
An alkali developer comprising an aqueous solution of about 0.1 to 5% by weight of an organic amine compound such as monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and diisopropanolamine is used.

The development is usually performed by immersion development, spray development, shower development, brush development, ultrasonic development, or the like.
Preferably about 10 to 60 ° C, more preferably 15 to 4 ° C.
It is performed at a temperature of about 5 ° C.

[0053]

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 invention.

Example 1 3 parts by weight of dipentaerythritol hexaacrylate as the ethylenically unsaturated compound as the component (A) and (D)
10 parts by weight of a methyl methacrylate (80 mol%) / methacrylic acid (20 mol%) copolymer as a polymer binder as a component is added to 80 parts by weight of propylene glycol monomethyl ether acetate, and the mixture is stirred and dissolved. After that, a red pigment as a coloring material of the component (F) C.I. I. Pigment Red 254 is added and dispersed,
Further, N as the sensitizing dye of the component (B)
o. 0.8 parts by weight of the coumarin compound shown in 2,
2,2′-bis (o) as a polymerization initiator of the component (C)
-Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 0.8 part by weight, 4,4'-bis (diethylamino) benzophenone 1.1 part by weight, and a hydrogen-donating compound of component (E) By adding and dissolving 0.4 parts by weight of 2-mercaptobenzothiazole as a coating solution for the photopolymerizable composition, and applying the coating solution for the photopolymerizable composition to a glass substrate with a spin coater. Then, by drying in an oven at 50 ° C. for 2.5 minutes, a photopolymerizable image forming material having a dried photopolymerizable composition layer having a thickness of 1.5 μm on a support was produced.

A step tablet and a resolving power chart are arranged on the photopolymerizable composition layer of the obtained photopolymerizable image forming material, and parallel rays of g-line and h-line by cutting i-line from a high-pressure mercury lamp as a light source Irradiation at an exposure of 100 mj / cm ² resulted in polymerization and curing to form a colored resin layer.

Subsequently, the colored resin layer was washed with an alkali developer comprising an aqueous solution containing 0.2% by weight of potassium carbonate and 0.2% by weight of a surfactant (“Lionox NC-100” manufactured by Lion Corporation). Development was performed by showering at 25 ° C. for 1 minute. As a result, a one-stage cured image was obtained as the step image, and a high-resolution image corresponding to the resolution chart was obtained.

Example 2 The coloring material of the component (F) was a green pigment C.I. I. Pigment Green 36, except that a photopolymerizable image forming material was prepared, exposed and developed in the same manner as in Example 1, and as a result, a one-stage cured image was obtained as a step image, and
A high-resolution image corresponding to the resolution chart was obtained.

Example 3 The coloring material of the component (F) was a blue pigment C.I. I. Pigment Blue 15: 6, except that a photopolymerizable image-forming material was prepared, exposed and developed in the same manner as in Example 1, and as a result, a two-stage cured image was obtained as a step image. In addition, a high-resolution image corresponding to the resolution chart was obtained.

Example 4 The polymerization initiator (C) was prepared by mixing 0.6 parts by weight of dicyclopentadienyltitanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] with 4,4'- 0.6 parts by weight of bis (diethylamino) benzophenone, the hydrogen-donating compound of the component (E), 0.6 parts by weight of ethyl N, N-dimethylaminobenzoate, and the coloring material of the component (F), Pigment C. I. Pigment Blue 15: 6, except that the photopolymerizable image-forming material was prepared, exposed and developed in the same manner as in Example 1, except that a two-step cured image was obtained. And a high-resolution image corresponding to the resolution chart was obtained.

Comparative Example 1 A photopolymerizable image-forming material was prepared and exposed in the same manner as in Example 1 except that the sensitizing dye of the component (B) was changed to the following ketocoumarin compound. As a result of the development, a one-stage cured image was not obtained as a step image, and the image corresponding to the resolving power chart was also inferior with a reduced film thickness.

[0061]

Embedded image

Comparative Example 2 A photopolymerizable image-forming material was prepared in the same manner as in Example 1 except that the sensitizing dye of the component (B) was not used.
As a result of exposure and development, a cured image of the step image was not obtained, and the image corresponding to the resolution chart was also extremely poor in film thickness reduction.

[0063]

According to the present invention, a photopolymerizable composition containing a coumarin compound as a sensitizing dye exhibits high sensitivity particularly to a visible light source in a short wavelength region and forms a colored relief image. It is possible to provide a photopolymerizable composition in which a decrease in color purity at the time is eliminated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 505 G03F 7/004 505 7/027 7/027 7/029 7/029 7/033 7 / 033 F term (reference) 2H025 AA00 AA01 AB03 AB09 AB13 AB15 AB16 AB17 AC01 AD01 BC31 BC51 CA01 CA20 CA27 CA28 CA39 CB10 CB13 CB43 CC11 FA03 FA17 4J011 PA67 PA68 PA69 PC02 PC08 QA03 QA04 QA12 QA13 QA14 SA23A UA01 UA06 WA01 4J026 AA43 AA45 AA48 AA49 AA50 BA26 BA27 BB01 DB06 DB15 FA05 GA06

Claims (7)

[Claims] 1. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) an ethylenically unsaturated compound (B) a sensitizing dye comprising a coumarin compound represented by the following general formula (I): [In the formula (I), R ¹ and R ² each independently represent an alkyl group which may have a substituent, and R ³ represents an alkyl group which may have a substituent, A cycloalkyl group which may have a substituent or an aryl group which may have a substituent. (C) Photopolymerization initiator 2. The compound of the formula (I) wherein R is
^The photopolymerizable composition according to claim 1, wherein ³ is an alkyl group. 3. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator as the component (C) is a hexaarylbiimidazole derivative. 4. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator as the component (C) is a titanocene derivative. 5. The photopolymerizable composition according to claim 3, further comprising a dialkylamino group-containing benzophenone derivative as a photopolymerization initiator of the component (C). 6. The photopolymerizable composition according to claim 1, further comprising a polymer binder (D). 7. The photopolymerizable composition according to claim 1, further comprising a coloring material (F) component.