JP2912140B2 - Photosensitive material for plate making - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for plate making, and more particularly to a photosensitive material having high sensitivity to ultraviolet light and visible light, and particularly suitable for image formation by a visible light laser. A photosensitive material for plate making using a photopolymerizable composition.

[0002]

2. Description of the Related Art Photosensitive compositions applicable to image recording or image formation include conventional resist materials for producing printed wiring boards, printing materials for resin relief printing plates and PS plates, and holograms. Widely used for recording materials. In recent years, the progress of electronics in plate making has been remarkable, and the light source for exposure
An exposure method using an ultraviolet light such as a carbon arc to a visible light laser, for example, an argon laser light has begun to be used. Currently, there are silver halide photographic materials and electrophotographic materials as photosensitive materials that can be used in such a system, but we want to form an image with the intended function directly without any intermediary to save labor. Therefore, development of a photosensitive material having high sensitivity to a visible light laser is desired.

For this reason, JP-A-59-189340, JP-A-62-263202 or PolymerPrep. 36 (3), 533 (19
87) and the like, the conventional general photosensitive composition is insufficient, so that a two-component photopolymerization initiator that becomes a specific organic dye and an organic peroxide is used. Attempts have been made to improve the light-sensitive characteristics by using such methods. However, even if such a two-component photopolymerization initiator is used, the sensitivity is not sufficient, and a more sensitive photopolymerization initiator can be used because a lower output laser can be used. It is desired to find out.

An object of the present invention is to provide a plate-making photosensitive material having high sensitivity to ultraviolet light and visible light.

[0005]

According to the present invention, there is provided a photosensitive material for plate making according to the present invention, in which a mask layer and a photosensitive layer are sequentially provided on a support, and the photosensitive layer comprises a three-component layer containing a specific fluoran compound or the like. It contains a system photopolymerization initiator,
The photosensitive layer is specifically composed of (1) a photopolymerizable compound having at least one ethylenically unsaturated bond, (2) a fluoran compound represented by the formula I, a rhodamine lactam compound or a xanthene compound.

[0006]

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(Where M is a carbon atom or a nitrogen atom,
When M is a nitrogen atom, A is an oxygen atom, M is a carbon atom
A is an oxygen atom or -NR₁₃(R₁₃Is replaced or
Represents an unsubstituted aryl group or heterocyclic group),
R₁, R_Two, R_Three, R_Four, R_Five, R₆, R ₇, R₈, R₉,
R_Ten, R₁₁, R₁₂Represents a hydrogen atom, a hydroxyl group, a C1-8
A substituted or unsubstituted alkyl group, alkoxyl group,
Reeloxyl group, araalkoxyl group, aralkyl
Or a substituted or unsubstituted alkyl having 1 to 8 carbon atoms
Groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.
Or an amino group substituted with a heterocyclic group,
To 8 substituted or unsubstituted alkyl groups, cycloalkyl
Or aryl, aralkyl, or heterocyclic groups.
A substituted amino group, substitution of 2 to 1 to 8 carbon atoms or
Unsubstituted alkyl, cycloalkyl, aryl,
Amino groups substituted with an aralkyl group or a heterocyclic group
Or a halogen atom, at least one of which is
A substituted or unsubstituted amino group or a halogen atom
And 3-substituted coumarin represented by formula II
With a halogenated sulfone compound of the formula III
Photosensitizer

[0008]

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Wherein Y is a cyano group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an araalkoxyl group, a heterocyclic group or -ZR ₁₉ (Z is a sulfonyl group,
A sulfinyl group or a carbonyl group, and R ₁₉ has 1 carbon atom
To 8 substituted or unsubstituted alkyl groups, alkoxyl groups, alkenyl groups, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, aryloxyl groups or heterocyclic groups), R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,
Alkoxyl group, araalkoxyl group, aralkyl group,
An amino group substituted with one substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group or heterocyclic group having 1 to 8 carbon atoms;
8 represents an amino group, a nitro group or a halogen atom substituted with a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group or heterocyclic group.) ArSO ₂ CX ₃ ... III Wherein Ar represents a substituted or unsubstituted aryl group, X represents a halogen atom), or (1) a photopolymerizable compound having at least one ethylenically unsaturated bond, (2 ) Fluoran compounds, rhodamine lactam compounds or xanthene compounds of the formula I

[0010]

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Wherein M is a carbon atom or a nitrogen atom;
When M is a nitrogen atom, A is an oxygen atom, M is a carbon atom
A is an oxygen atom or -NR₁₃(R₁₃Is replaced or
Represents an unsubstituted aryl group or heterocyclic group),
R₁, R_Two, R_Three, R_Four, R_Five, R₆, R ₇, R₈, R₉,
R_Ten, R₁₁, R₁₂Represents a hydrogen atom, a hydroxyl group, a C1-8
A substituted or unsubstituted alkyl group, alkoxyl group,
Reeloxyl group, araalkoxyl group, aralkyl
Or a substituted or unsubstituted alkyl having 1 to 8 carbon atoms
Groups, cycloalkyl groups, aryl groups, aralkyl groups, etc.
Or an amino group substituted with a heterocyclic group,
To 8 substituted or unsubstituted alkyl groups, cycloalkyl
Or aryl, aralkyl, or heterocyclic groups.
Represents a substituted amino group or halogen atom.
At least one of them is a substituted or unsubstituted amino group or amino group.
(3) a thione represented by the formula IV
Xanthone compounds and organic peroxides

[0012]

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(Wherein R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ ,
R ₂₅ , R ₂₆ and R _{27 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a cyano group,
-COOR ₂₈ (R ₂₈ represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group having 1 to 8 carbon atoms) or a halogen atom. .

Here, the addition polymerizable compound having at least one ethylenically unsaturated bond is a monomer, an oligomer or a polymer having an ethylenically unsaturated bond, such as n-butyl acrylate, Cyclohexyl acrylate, hydroxyethyl acrylate, 2
-Butoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate
Acryloxyethyl phosphate, acryloxypropyl phosphate, ethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-propanediol diacrylate 1,6-hexanediol-diacrylate, neopentylglycol-diacrylate
Resorcinol diacrylate, hydroquinone diacrylate, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, Bis (acryloxyethyl) phosphate, sorbitol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pyrogallol triacrylate
Acrylates such as pentaerythritol tetraacrylate, pentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate -Phenyl, phenyl methacrylate, 2-
Hydroxyethyl methacrylate, methacryloxyethyl phosphate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid,
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, dipropylene glycol dimethacrylate, neopentyl glycol dimethacrylate,
1,6-hexanediol-dimethacrylate, 2,2 '
-Bis (4-methacryloxydiethoxyphenyl) propane, 2,2'-bis (4-methacryloxypentaethoxyphenyl) propane, bis (methacryloxyethyl) phosphate, bis (methacryloxypropyl) phosphate Sorbitol dimethacrylate,
Hydroquinone dimethacrylate, resorcin dimethacrylate, sorbitol trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaeryth Methacrylates such as litholtetramethacrylate, dipentaerythritolhexmethacrylate, dipentaerythritolpentamethacrylate, acrylamide, diacetoneacrylamide, N-diethylacrylamide, N, N- Methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, methacrylamide, N, N-methylenebismethacrylamide, 1,6-
Amides such as hexamethylenebismethacrylamide and xylinbismethacrylamide, α-methylstyrene, P-
Divinylbenzene, 1- (2-diethylaminoethyl)
-4-vinylbenzene, allylacetic acid, allylacetone,
Allyl alcohol, allylbenzene, vinylpyridine,
Examples include N-vinyl-2-pyrrolidone, diethyl itaconate, diallyl itaconate, monobutyl itaconate, diallyl maleate, diallyl fumarate, N-lauryl maleimide and the like. These may be used alone or in combination of two or more. The amount of the compound (1) used is
It is 10 to 40% by weight based on the total composition.

The compound represented by the general formula I includes 3-
Diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-isobutylethylamino-6-methyl-
7-anilinofluoran, 3-isobutylethylamino-7-anilinofluoran, 3-cyclohexylmethylamino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-thimer-7-anilinofur Oran, 3-
Isohexylethylamino-fluoran, 3-isohexylethylamino-6-methyl-7-anilinofluoran, 3-N-ethyl-N- (P-methylphenyl) amino-7- (P-acetylanilino) Fluoran, 3-pyrrolidino-7- (P-acetylanilino) fluoran,
3-hexamethyleneimino-6-methyl-7- (m-acetylanilino) fluoran, 2-anilino-3-ethoxy-6-diethylaminofluoran, 2-anilino-
3-ethoxy-6-di-n-butylaminofluoran,
3-diethylamino-5-methyl-7-dibenzylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-p-methylbenzylethylamino-7-benzylethylaminofluoran, 3-diethylamino-6 -Methyl-7-benzylethylaminofluoran, 3-diethylamino-6-methyl-7- (2,4
-Dimethylbenzyl) methylaminofluoran, Papyrrol SD-120 (trade name, manufactured by Showa Denko KK), 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluoran , 3-isobutylethylamino-7- (o-chloroanilino) fluoran, 3-diethylamino-7- (p-chloroanilino)
Fluoran, 3- (N-ethyl-N-isopentyl) amino-7- (o-chloroanilino) fluoran, 3-
(N, N-diisopentyl) amino-7- (o-chloroanilino) fluoran, 3-di-n-butylamino-6
-Methyl-7-p-chlorophenylaminofluoran,
Fluoran compounds such as 3-diethylamino-6-methyl-7-o-chlorophenylaminofluoran, rhodamine-B-anilinolactone, rhodamine-Bp-nitroanilinolactone, rhodamine Bo- Rhodamine lactam compounds such as chloroanilinolactone, React Red 44
8 (trade name, manufactured by BASF) and the like. These may be used alone or in combination of two or more.

The compound represented by the general formula II includes 3-
Cyanocoumarin, 3-acetylcoumarin, 3-methoxycarbonylcoumarin, 3-cyclohexylcarbonylcoumarin, 3-ethynylcarbonylcoumarin, 3-phenoxycarbonylcoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 3- (2- Benzimidazolyl) -7-diethylaminocoumarin, 3-
(2-benzothiazolyl) -4-cyano-diethylaminocoumarin, 3- (5-chloro-2-benzothiazolyl) -7-diethylaminocoumarin, 3- (4-chlorophenyl) -4-methyl-7-diethylaminocoumarin, 3- ( 4-acetylaminophenyl) -4-methyl-7-diethylaminocoumarin, 7-methoxy-3-phenylsulfonylcoumarin, 7-methoxy-3-phenylsulfinylcoumarin, 3-benzoylcoumarin, 3
-(4-cyanobenzoyl) -coumarin, 3-acetyl-7-dimethylaminocoumarin, 3-benzoyl-7-
Dimethylaminocoumarin, 3-thienylcarbonylcoumarin, 3-thienylcarbonyl-7-methoxycoumarin, 7-diethylamino-3-coumarinoylacetate
G, 3-cinnamoyl-7-diethylaminocoumarin,
3,3'-carbonylbis (7-diethylamino) coumarin, 3,3'-carbonylbis (5,7-dimethoxy) coumarin, 3,3'-carbonylbis-5,7-dimethoxycoumarin, 3,3'- Carbonyl bis (4-cyano-7-diethylamino) coumarin, 3- (2-benzimidazoyl) -7-diethylaminocoumarin, 3-
(2-benzoxazoyl) -7-diethylaminocoumarin, 7-diethylamino-5 ′, 7′-dimethoxy-
3,3'-carbonylbiscoumarin and the like.

Examples of the halogenated sulfone compound represented by the general formula III include trichloromethylphenyl sulfone,
Tribromomethylphenylsulfone, trichloromethyl-p-chlorophenylsulfone, tribromomethyl-p
-Nitrophenyl sulfone, 2-trichloromethylbenzothiazole sulfone, 2,4-dichlorophenyltrichloromethyl sulfone, 2-methyl-4-chlorophenyltrichloromethyl sulfone, 2,5-dimethyl-4-
Chloromethyl sulfone, 2,4-dichlorophenyl tribromomethyl sulfone and the like can be mentioned.

Examples of the thioxanthone compound represented by the general formula IV include 2-methyloxanthon, 2-isopropylthioxanthone, 2-ethyloxanthone, 2-chlorothioxanthone, 2-ethoxycarbonyloxanthone, and 2-t-butyloxanthone. , 2-t-butyl-4
-Methylthioxanthone, 1-cyano-3-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4
-Diethylthioxanthone, 2,4-diisopropylthioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, 2-methyl-6-morpholinomethyl- Thioxanthone, N-octyl-thioxanthone-
3,4-dicarboximide, N- (1,1 ′, 3,
3'-tetramethylbutyl-thioxanthone-3,4-
Dicarboximide, 1-ethoxycarbonyl-3-aminothioxanthone and the like.

As the organic peroxide, methyl ketone
Oxide, cyclohexanone peroxide, acetylacetone peroxide, t-butyl peroxide, 1,1 ', 3,3'-tetramethylbutyl hydroperoxide, 2,2'-bis (t-butylperoxy) butane 1,1-bis (t-butylperoxy) cyclohexane, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butylperoxide
Oxide, di (t-butylperoxy) isophthale
, Α, α-bis (t-butylperoxyisopropyl) benzene, di (t-butylperoxy) terephthalate, di (t-butylperoxy) phthalate, t-butylcumylperoxide, t-butylperoxide -Oxybenzoate, t-butyl peroxylaurate, t-butyl peroxy neodecanoate, 2,5-dimethyl-
2,5- (dibenzoylperoxy) hexane, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexane, 3,3 ', 4,4'-tetra- (t-butylper-
(Oxycarbonyl) benzophenone, 2,4-dichlorobenzoyl peroxide, di-2-ethylhexylperoxycarbonate, t-butylperoxypropylcarbonate, di (3-methyl-3-methoxybutyl) ) Peroxycarbonate, 3,5,5-trimethylhexanoyl peroxide and the like.

The amount of each of the above substances is determined by the amount of the compound of the formula I / the formula
In the system of the compound of the formula II / the compound of the formula III, 1 to 20 parts by weight of the compound of the formula I, 1 to 30 parts by weight of the compound of the formula II,
1 to 20 parts by weight of the compound of III, the photosensitive composition 1
The sum of the three components is used in an amount of 1 to 30 parts by weight based on 00 parts. In the system of the compound of formula I / compound of formula IV / organic peroxide, 100
The compound of the formula I is 1 to 20 parts by weight, the compound of the formula IV is 1 to 30 parts by weight, the organic peroxide is 1 to 20 parts by weight, and the photosensitive composition is 100 parts by weight. The sum of the three components is used in a proportion of 1 to 30 parts by weight.

In the photosensitive layer of the plate-making photosensitive material of the present invention, an organic polymer binder, if necessary,
A thermal polymerization inhibitor, a plasticizer and the like can be added. The organic polymer binder may be appropriately selected depending on various purposes of improvement such as compatibility, film forming property, developability, chemical resistance and the like. For example, when water development is possible, gelatin, sodium alginate, methylcellulose, carboxycellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, polyvinylalcohol,
Aqueous solutions such as polyvinyl thiomer ether, vinyl methyl ether-maleic anhydride copolymer, polyethylene oxide, polyacrylic acid soda, partially saponified polyacrylate, polyacrylamide, acrylamide-diacetone acrylamide copolymer, etc. When a hydrophilic resin can be used and alkaline development is possible, acrylic acid-methacrylic acid ester copolymer, 2-hydroxyethyl methacrylate-acrylonitrile-methyl methacrylate-methacrylic acid copolymer, styrene-maleic anhydride copolymer An alkali-soluble resin such as a coalesced partial ester compound, polyvinyl-p-hydroxybenzal, a novolak-type phenol resin, and polyhydroxystyrene can be used. When acid development is possible, dimethylaminoethyl methacrylate is used.
An acid-soluble resin such as an ethyl methacrylate copolymer can be used. To improve film strength and adhesion, polyvinyl acetate,
Vinyl chloride vinyl acetate copolymer, acrylonitrile-styrene copolymer, acrylonitrile-vinyl chloride-vinyl chloride copolymer, chlorinated polyolefin-vinyl chloride-vinyl acetate copolymer, polyethylene fine particles, polystyrene, polyurethane, acetyl cellulose Polyvinyl butyral, polyamide and polyethylene terephthalate isophthalate can be used. The amount of the polymer binder used is 300 parts by weight or less based on 100 parts by weight of the ethylenically unsaturated bond-containing compound.

Examples of the thermal polymerization inhibitor include hydroquinone,
Examples thereof include hydroquinone monomethyl ether, p-methoxyphenol, pyrogallol, t-butylcategorol, chloranil, and 2-hydroxybenzphenone. The amount of these thermal polymerization inhibitors used is 0.005 to 100 parts by weight of the ethylenically unsaturated bond-containing compound.
3 parts by weight.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, and triethylene glycol dicaprylate.
Dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate
And dibutyl maleate-triacetylglycerin. These plasticizers are used in an amount of 0.1 to 8 parts by weight per 100 parts by weight of the ethylenically unsaturated bond-containing compound.
Parts by weight.

The mask layer of the photosensitive material for plate making according to the present invention may be made of an inorganic pigment such as carbon, graphite, titanium oxide, chromium yellow or iron oxide as a coloring agent, Varifast Orange 3206, Varifast Yellow 3104, and Eizen Spiron Yellow GRH. Dye Resin Yellow F, Zapon Fast Orange RR, Aizen Spiron Orange 2RH, Aizen Spiron Red BEH, Aizen Spiron GEH, Varifast Black 3804, Varifast Black 1802, and the like. However, for the purpose of the present invention, it is preferable to select a material having high light-shielding properties and good weather resistance.

As the binder of the mask layer, it is preferable to be able to develop with one solution at the time of development, and therefore, an organic polymer binder used for the photosensitive layer may be used. Examples of the solvent for dissolving or dispersing the photosensitive layer or the mask layer include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dibutyl ketone: ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, dimethyl phthalate, and ethyl benzoate. Esters such as: aromatic hydrocarbons such as toluene, xylene, and monochlorobenzene: halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, trichloroethine, and perchlorethylene: air such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve Ters: dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like. However, when the photosensitive layer is formed on the mask layer, the solvent should not be mixed so that the photosensitive composition solution dissolves the mask layer.

As the support of the photosensitive material for plate making of the present invention, for example, polypropylene, polyvinyl chloride, polycarbonate
Transparent sheets or films such as bone, polyethylene terephthalate, polyvinyl acetal, nylon, polyamide, polyimide, regenerated cellulose, cellulose triacetate and the like can be used. The photosensitive resin layer further has a transparent cover which can be peeled off on the photosensitive layer or has a low oxygen permeability in order to suppress a decrease in sensitivity due to oxygen, prevent blocking, and impart surface smoothness of the exposed surface. An overcoat layer made of a water-soluble or alkali-soluble resin or the like may be provided.

Exposure light sources applicable to the plate-making photosensitive material of the present invention include carbon arc lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, tungsten lamps, and the like.
Examples include a fluorescent lamp, an argon ion laser, a helium neon laser, a semiconductor laser, a ruby laser, an alexan dry laser, and a gold vapor laser.

[0028]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Composition of coating solution for mask layer 5 g of methacrylic acid-methacrylic acid ester copolymer (30 mol% of methyl methacrylate, 40 mol% of 2-hydroxyethyl methacrylate, 27 mol% of methacrylonitrile, 3 mol% of methacrylic acid 5 g of carbon black (MA-100 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 90 g of methylcellosolve 0.2 g of silicone-based surfactant (FS-XB-2725 manufactured by Dow Corning Co., Ltd.) And the mixture was shaken and dispersed with a paint shaker for 6 hours to obtain a coating solution for the mask layer. This coating solution was applied to a 100 μm thick polyethylene terephthalate film support having been subjected to a corona discharge treatment using a wire bar, and dried with warm air at 90 ° C. for 90 seconds. A mask layer of 0.5μ was formed.

Composition of Coating Solution for Photosensitive Layer Acrylic acid-methacrylic acid ester copolymer solution 10 g (NK-3, manufactured by Ryo Kagaku Kogyo Co., Ltd.) Trimethylolpropane triacrylate 3 g Photopolymerization initiator ((I), (II) , (III)) (I) Fluoran compound (ATP manufactured by Yamada Chemical Industry) 0.1 g (II) 3,3'-carbonylbis (7-diethylaminocoumarin) 0.1 g (III) α, α, α-tribromo Methylphenyl sulfone 0.1 g p-methoxyphenol 0.01 g toluene 35 g methyl ethyl ketone 25 g The above coating solution was applied on the above mask layer using a wire bar, and dried with 90 ° C. hot air for 60 seconds. A photosensitive layer having a coating thickness of about 1.5 μ was formed on the mask layer.

Overcoat layer coating solution composition Polyvinyl alcohol 3 g (Nippon Synthetic Chemical Industry Gosenol NH-20) Distilled water 90 g And the above overcoat coating solution The photosensitive layer is coated with a wire bar and dried with warm air at 90 ° C. for 60 seconds to form an overcoat layer having a thickness of about 0.5 μm on the photosensitive layer. A sample was prepared. Measurement of Sensitivity In the photosensitivity test, a step tablet (Step Tablet No. 2 manufactured by Kodak Co., Ltd.) was closely attached to a polyethylene terephthalate film sample, and an interference filter (Kenko Co., Ltd.) was used with a 2 kW ultra-high pressure mercury lamp as a light source. BP-49) for 10 seconds. The light intensity on the exposed surface measured with an optical power meter (TQ8210 manufactured by Advantest Co., Ltd.) using a sensor (TQ82017) having a spectral sensitivity at 488 nm was 1 mW / cm ² . And 0.0 at 30 ° C.
A 1% anhydrous sodium carbonate aqueous solution was used as a developing solution and left standing for 30 seconds in the developing solution to elute the uncured portion and the mask layer, and the sensitivity of the photosensitive material for plate making was determined by the number of steps of the step tablet. The higher the number of stages, the higher the sensitivity.
The number of photocured stages of this sample was 5.

Scanning recordability with argon ion laser Argon ion laser (manufactured by NEC, water-cooled)
The light was condensed to a beam diameter of 25 μm on the surface of the sample through a filter (× 4) (manufactured by Kenko Corporation), and scanning exposure was performed at a light intensity of 2.3 mW and a scanning speed of 3.1 m / s. As a result, a colored image having a line width of about 30 μm was obtained. Examples 2 to 5 Samples were prepared in the same manner as in Example 1 except that the fluoran compound in Example 1 was changed as shown in Table 1, and the sensitivity was measured. The scanning recordability by an argon ion laser was also performed in the same manner as in Example 1 to obtain colored images having a line width of about 25 μm or more. Examples 6 to 30 The fluoran compound in Example 1 was changed and a combination of a thioxanthone compound (IVa or IVb) and an organic peroxide (Va or Vb) was used as a photosensitizer. To prepare a sample, and the sensitivity was measured. The scanning recordability by an argon ion laser was also performed in the same manner as in Example 1 to obtain colored images having a line width of about 25 μm or more. The results are shown in Tables 1 to 3 including the results of Example 1.

The sensitivity of each sample of Examples 1, 13, 18, 19, and 25 was measured using an interference filter (KIRL-78, manufactured by Kenko Corporation) with the same light source as in Example 1. Was performed. The light intensity on the exposed surface measured with an optical power meter (TQ8210 manufactured by Advantest Co., Ltd.) using a sensor (TQ82017) having a spectral sensitivity at 780 nm was 1.7 mW / cm ² . The number of photocured steps of the sample developed in the same manner as in Example 1 is shown in parentheses in the column of sensitivity in Table 1. Comparative Examples 1 to 24 The photopolymerization initiator was a two-component system, and the amount of each component used was 0.1.
A sample was prepared in the same manner as in Example 1 except for 15 g,
The sensitivity was measured.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

In Tables 1 to 3, Ia to Io are fluoran compounds and the structures are shown in Tables 4 to 8. Also
II-a is 3,3′-carbonylbis (7-diethylaminocoumarin), II-b is 3- (4-cyanobenzoyl)
Indicates -5,7-dimethoxycoumarin. III-a is α,
α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron and Steel Chemical Industry Co., Ltd.) and III-b indicate 2,4-dichlorophenyltribromomethylsulfone. IV-a is 2,4-
Diethyloxanthon, IV-b represents 2-chlorothioxanthone. Va is benzoyl peroxide, Vb
Represents 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone.

As shown in Table 1, these examples were higher in sensitivity and superior to the conventionally known systems using 3-ketocoumarin and N-phenylglycine.

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

As shown in the above examples, the photosensitive material for plate making of the present invention has a high sensitivity to ultraviolet light or visible light and can form a colored image with a laser having a lower energy. It becomes possible and is effective as a photosensitive material for plate making.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-15503 (JP, A) JP-A-63-180946 (JP, A) JP-A-55-13780 (JP, A) 137876 (JP, A) JP-A-62-143043 (JP, A) JP-A-61-94040 (JP, A)

Claims (2)

(57) [Claims] A mask layer and a photosensitive layer are sequentially provided on a support, wherein the photosensitive layer comprises: (1) an addition-polymerizable compound having at least one ethylenically unsaturated bond, and a photosensitizer comprising : 2) a fluoran compound, a rhodamine lactam compound or a xanthene compound represented by the formula I (In the formula, M is a carbon atom or a nitrogen atom, A is an oxygen atom when M is a nitrogen atom, A is an oxygen atom when M is a carbon atom, or -NR ₁₃ (R ₁₃ is a substituted or unsubstituted aryl- R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R 7, R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R _{12 each} represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an aryl group; Roxyl group, araalkoxyl group, aralkyl group, 1 to 8 carbon atoms
An amino group substituted with a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group or heterocyclic group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, cycloalkyl Group, an aryl group, an aralkyl group or a heterocyclic group, represents an amino group or a halogen atom, at least one of which is a substituted or unsubstituted amino group or a halogen atom); 3-substituted coumarin represented (In the formula, Y is a cyano group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an araalkoxyl group, a heterocyclic group, or -ZR ₁₉ (Z is a sulfonyl group, a sulfinyl group, or a carbonyl group; R ₁₉ represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an alkenyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, an aryloxyl group or a heterocyclic group. ,
R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R _{18 each} represent a hydrogen atom,
8 substituted or unsubstituted alkyl group, alkoxyl group, aralkoxyl group, aralkyl group, 1 substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, cycloalkyl group, aryl group, aralkyl group or heterocyclic group Amino group substituted with a ring group, two substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, cycloalkyl group, aryl group, aralkyl group or amino group substituted with a heterocyclic group, nitro group Or a halogen atom) and formula II
Containing a halogenated sulfone compound Ar-SO ₂ CX ₃ ... III (wherein Ar represents a substituted or unsubstituted aryl group and X represents a halogen atom) ; A photosensitive material for plate making, comprising a colorant and a binder. 2. A mask layer and a photosensitive layer are sequentially provided on a support, wherein the photosensitive layer comprises: (1) a photopolymerizable compound having at least one ethylenically unsaturated bond ; 2) Fluoran compounds, rhodamine lactam compounds or xanthene compounds of the formula I (In the formula, M is a carbon atom or a nitrogen atom, A is an oxygen atom when M is a nitrogen atom, A is an oxygen atom when M is a carbon atom, or -NR ₁₃ (R ₁₃ is a substituted or unsubstituted aryl- R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R 7, R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R _{12 each} represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, an aryl group; Roxyl group, araalkoxyl group, aralkyl group, 1 to 8 carbon atoms
An amino group substituted with a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group or heterocyclic group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, cycloalkyl Group, an aryl group, an aralkyl group, or an amino group or a halogen atom substituted with a heterocyclic group, at least one of which is a substituted or unsubstituted amino group or a halogen atom); Thioxanthone compound represented by (Wherein, R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ ,
R ₂₇ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a cyano group, —COOR ₂₈
Wherein R ₂₈ represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group having 1 to 8 carbon atoms or a halogen atom, and an organic peroxide , and the mask layer contains A photosensitive material for plate making characterized by comprising a binder.