JPH0962001A - Waterless photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a waterless planographic printing plate having high sensitiv ity for active rays in a wide region from UV rays to visible rays by incorporat ing a specified compd. and an oximether compd. into a photopolymerizable photosensitive layer. SOLUTION: A primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer are deposited in this order on a supporting body. The photopolymerizable photosensitive layer contains a compd. having a photopolymerizable ethylene-type unsatd. group and an oximether compd. In this case, the compd. having a photopolymerizable ethylene-type unsatd. group which can be used is a monomer, oligomer or macromer having at least one photopolymerizable ethylene-type unsatd. group. Further, the oximether compd. used is a compd. expressed by formula (R<1> ) (R<2> )C=N-OR<3> , wherein R<1> =R<3> are same or different univalent org. residues.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate which does not require a fountain solution, and more specifically, it is formed by laminating a primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer on a support in this order. It relates to a water-free photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventional printing methods that require dampening water make it difficult to control the delicate balance between dampening water and ink.
There have been major problems such as emulsification of the ink and mixing of the ink with the fountain solution, resulting in defective ink density and scumming, which causes wasted paper. On the other hand, a fountain solution-free photosensitive lithographic printing plate (hereinafter referred to as a waterless planographic printing plate) has many advantages because it does not require a fountain solution. Regarding waterless planographic printing plates for performing lithographic printing without using such dampening water, for example, JP-B-44-23042, JP-B-46-16044, JP-B-54-26923, and JP-B-56- 14976, Japanese Patent Publication No. 56-23150, Japanese Patent Publication No. 61-54222,
JP-A-58-215411, JP-A-2-16561
In Japanese Patent Application Laid-Open No. 2-236550, various types have been proposed. Among them, on the support, a primer layer,
A photopolymerizable photosensitive layer and a silicone rubber layer are applied in this order, and by exposure, the photopolymerizable photosensitive layer in the exposed portion is polymerized and cured, and the adhesive force with the silicone rubber layer is strengthened,
A waterless planographic printing plate which forms an image portion by peeling off only the unexposed silicone rubber layer in development has extremely excellent performance.

On the other hand, in recent years, due to rapid advances in output systems such as prepress systems, imagesetters, and laser printers, new plate making methods for computer tow plates, computer tow cylinders, etc. have been proposed, and for these printing systems. A new type of printing material is desired and is being developed.

[0004]

However, a printing material having a sufficient sensitivity to a visible light laser has not yet been found, and the waterless planographic printing plate described above is also not found.
Compared with sensitivity to UV light of 0 nm or less, 400 nm
The above sensitivity to visible light is extremely low. The present inventors have accomplished the present invention as a result of intensive research to provide a waterless planographic printing plate that does not have such drawbacks.

That is, the object of the present invention is to provide a waterless lithographic printing plate having high sensitivity, particularly a waterless lithographic printing plate having high sensitivity to actinic rays in a wide range of ultraviolet rays to visible light. .

[0006]

The above-mentioned objects of the present invention are achieved by the following constitutions. That is, on the support,
A primer layer, a photopolymerizable photosensitive layer, and a silicone rubber layer are laminated in this order, and the photopolymerizable photosensitive layer has the following components.
A photosensitive lithographic printing plate which does not require a fountain solution, which comprises i) and ii).

I) Compound having a photopolymerizable ethylenically unsaturated group ii) Oxime ether compound The present invention is described in detail below. The waterless planographic printing plate is usually required to have flexibility so that it can be set in a printing machine, and at the same time to be able to withstand a load applied during printing.
Representative supports having such requirements that can be used in the present invention include, for example, coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber, or a composite thereof. More preferably aluminum and aluminum-containing alloys (eg silicon, copper, manganese,
Alloys of aluminum with metals such as magnesium, chromium, zinc, lead, bismuth, and nickel).

In the present invention, a primer layer is provided between the support and the photosensitive layer. As the primer layer, various types can be used for the purpose of improving the adhesion between the support and the photopolymerizable photosensitive layer, preventing halation, dyeing an image and improving printing characteristics. For example, JP-A-60-2
Various photosensitive polymers as disclosed in Japanese Patent No. 2903, which are exposed and cured before laminating a photosensitive resin layer, and epoxy resins disclosed in Japanese Patent Laid-Open No. 62-50760 are heated. What is cured, JP-A-63-
The one disclosed in JP-A No. 133151, which has a hardened gelatin, and the one using a urethane resin and a silane coupling agent, which are disclosed in JP-A-3-200965, and the one disclosed in JP-A-3-273248. Examples of the urethane resin include
In addition, those obtained by hardening gelatin or casein are also effective. Furthermore, for the purpose of softening the primer layer,
Polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / butadiene rubber, polyisoprene, acrylate rubber, polyethylene having a glass transition temperature below room temperature in the primer layer. Polymers such as chlorinated polyethylene and chlorinated polypropylene may be added. The addition ratio is arbitrary, and the primer layer may be formed only with the additive as long as it is within the range in which the film layer can be formed. In addition, in accordance with the above-mentioned purpose, these primer layers have a dye, a pH indicator, a printout agent, a photopolymerization initiator, an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling agent). Agents, aluminum coupling agents), pigments, and additives such as silica powder and titanium oxide powder. After the application, it can be cured by exposure.

In general, the coating amount of the primer layer is suitably in the range of 0.1 to 20 g / m ² in terms of dry weight, preferably 1 to 10 g / m ² , and more preferably 1 to 5 g / m ^2.
m ² . The photopolymerizable photosensitive layer in the invention contains at least (i) a compound having a photopolymerizable ethylenically unsaturated group, and (ii) an oxime ether compound, and (iii) a high film-forming ability, if necessary. It contains a molecular compound and (iv) a photopolymerization initiator.

Component (i): A compound having a photopolymerizable ethylenically unsaturated group will be described. The above compound that can be used in the present invention is usually a monomer having at least one photopolymerizable ethylenically unsaturated group,
Oligomers or macromers, such as (A) alcohols (eg, ethanol, propanol, hexanol, 2-ethylhexanol, cyclohexanol, glycerin, hexanediol, trimethylolpropane, pentaerythritol, sorbitol, triethylene glycol, polyethylene glycol) Acrylic acid or methacrylic acid ester of polypropylene glycol, ω-methoxy polyethylene glycol, etc. (B) amines (eg, ethylamine, butylamine, benzylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, xylylenediamine, ethanolamine, aniline, etc. ) With glycidyl acrylate, glycidyl methacrylate or allyl glycidyl, (C) Reaction products of rubonic acids (eg, acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) with glycidyl acrylate, glycidyl methacrylate or allyl glycidyl , (D) amide derivatives (for example, acrylamide, N-methylol acrylamide, t-butyl acrylamide, methylene bis acrylamide, diacetone acrylamide, etc.), and the like. JP-B-48-41708 and JP-B-50- 603
No. 4, urethane acrylates as described in JP-A-51-37193, JP-A-48-6418.
No. 3, JP-B-49-43191, JP-B-52-304
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, which are described in US Pat. No. 90, US Pat. No. 4,540,649. Mention may be made of N-methylol acrylamide derivatives. Furthermore, Japan Adhesives Association Magazine Vol. 20, No.
7, those described as photocurable monomers and oligomers on pages 300 to 308 (1984),
P.Dreyfuss & RPQuirk, Encycl.Polym.Sci.Eng., 7,
The macromer monomers described in 551 (1987), Kagaku Kogyo, 38, 56 (1987), Kogaku Kogaku, 35, 262 (1986) and the like can also be used. However, the unsaturated group may be present in a mixture of acryl, methacryl, allyl, vinyl groups and the like, without being limited thereto. In addition, these may be used alone or in combination.

The following examples can be given as useful monomers used in the present invention.

[0012]

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[0013]

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The amount used is 5% by weight to 80% by weight, preferably 20% by weight to 70% by weight, based on the total solid content of the photopolymerizable photosensitive layer. Component ii): The oxime ether compound will be described.
The oxime ether compound of the component ii) used in the present invention is a compound represented by the following general formula [I].

(R ¹ ) (R ² ) C═N—O—R ³ [I] In the formula, R ¹ , R ² and R ³ represent the same or different monovalent organic residues. In the general formula [I], R ¹ and R ² are more preferably the same or different from each other, and may have a hydrogen atom, a halogen atom or a substituent, and may have an unsaturated bond. Hydrogen group, heterocyclic group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group,
Amino group, substituted amino group, substituted carbonyl group, carboxylate group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group, substituted phosphonato group, cyano group, nitro group Further, R ¹ and R ² may be bonded to each other to form a ring.

R ³ may have a substituent, and
It represents a hydrocarbon group or a heterocyclic group which may contain an unsaturated bond, and R ³ and R ² may be bonded to each other to form a ring. Next, examples of R ¹ , R ² and R ^{3 in} the general formula [I] are shown below. The hydrocarbon group which may have the above-mentioned substituent and may contain an unsaturated bond includes an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group and an alkynyl group. Groups and substituted alkynyl groups.

The alkyl group has 1 to 2 carbon atoms.
Examples thereof include a linear, branched, or cyclic alkyl group up to 0, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2-norbornyl be able to. Among these, straight-chains having 1 to 12 carbon atoms, 3 to 12 carbon atoms.
And branched alkyl groups having 5 to 10 carbon atoms are more preferable.

The substituted alkyl group includes a substituent and an alkylene group.
And the substituent is one except hydrogen.
A non-valent non-metallic atomic group is used.
Halogen atom (-F, -Br, -Cl, -I), hydroxy
Sil group, alkoxy group, aryloxy group, mercapto
Group, alkylthio group, arylthio group, alkyldithio
Group, aryldithio group, amino group, N-alkylamino
Group, N, N-dialkylamino group, N-arylamino
Group, N, N-diarylamino group, N-alkyl-N-
Arylamino group, acyloxy group, carbamoyloxy
Si group, N-alkylcarbamoyloxy group, N-ary
Rucarbamoyloxy group, N, N-dialkylcarbamo
Yloxy group, N, N-diarylcarbamoyloxy
Group, N-alkyl-N-arylcarbamoyloxy
Group, alkylsulfoxy group, arylsulfoxy group,
Silthio group, acylamino group, N-alkyl acylamido
Group, N-arylacylamino group, ureido group, N '
-Alkylureido group, N ', N'-dialkylurei group
Group, N'-arylureido group, N ', N'-diali
Ureido group, N'-alkyl-N'-aryluree
Id group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N '
-Alkyl-N-arylureido group, N ', N'-di
Alkyl-N-alkylureido group, N ', N'-dia
Alkyl-N-arylureido group, N'-aryl-N
-Alkyl ureido group, N'-aryl-N-aryl
Ureido group, N ', N'-diaryl-N-alkyl
RAID group, N ', N'-diaryl-N-aryluree
Id group, N'-alkyl-N'-aryl-N-alkyl
Luureido group, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-NA
Reyloxycarbonylamino group, N-aryl-NA
Lucoxycarbonylamino group, N-aryl-N-ali
-Carbonyloxyamino group, formyl group, acyl group,
Carboxyl group and its conjugate base group (hereinafter, carboxy group)
), Alkoxycarbonyl group, aryloxy
Sicarbonyl group, carbamoyl group, N-alkylcarba
Moyl group, N, N-dialkylcarbamoyl group, N-a
Lille carbamoyl group, N, N-diarylcarbamoy
Group, N-alkyl-N-arylcarbamoyl group,
Rukylsulfinyl group, arylsulfinyl group,
Killsulfonyl group, arylsulfonyl group, sulfo group
(-SO_ThreeH) and its conjugated base group (hereinafter, sulfonato
Group), alkoxysulfonyl group, aryloxys
Rufonyl group, sulfinamoyl group, N-alkylsulfate
Inamoyl group, N, N-dialkylsulfinamoyl
Group, N-arylsulfinamoyl group, N, N-diary
Sulfinamoyl group, N-alkyl-N-aryl
Sulfinamoyl group, sulfamoyl group, N-alkyl
Sulfamoyl group, N, N-dialkylsulfamoyl
Group, N-arylsulfamoyl group, N, N-diaryl
Rusulfamoyl group, N-alkyl-N-arylsulfur
Famoyl group, N-acylsulfamoyl group and their combination
Role base group, N-alkylsulfonylsulfamoyl group
(-SO₂NHSO₂(Alkyl)) and its conjugate base
Group, N-arylsulfonylsulfamoyl group (—SO
₂NHSO₂(Allyl)) and its conjugate base group, N-
Alkylsulfonylcarbamoyl group (-CONHSO₂
(Alkyl)) and its conjugated base group, N-aryls
Ruphonylcarbamoyl group (-CONHSO₂(All
l)) and its conjugate base group, alkoxysilyl group (-S
i (Oalkyl)_Three), An aryloxysilyl group (—S
i (Oallyl)_Three), Hydroxysilyl group (-Si
(OH)_Three) And its conjugate base group, phosphono group (—PO_Three
H₂) And its conjugated base group (hereinafter referred to as phosphonate group)
), A dialkylphosphono group (-PO_Three(Alky
l)₂), A diarylphosphono group (-PO_Three(Aryl)
₂), An alkylarylphosphono group (—PO_Three(Alky
l) (aryl)), monoalkylphosphono group (-PO
_ThreeH (alkyl)) and its conjugated base group (hereinafter referred to as
A monoarylphosphono group)
(-PO_ThreeH (aryl)) and its conjugated base group (hereinafter
Later called arylphosphonato group), phosphonooxy group
(-OPO_ThreeH₂) And its conjugated base group (hereinafter referred to as phosphona
Tooxy group), dialkylphosphonooxy group (-
OPO_Three(Alkyl)₂), Diarylphosphonooxy
Group (-OPO_Three(Aryl)₂), Alkyl aryl phos
Honoxy group (-OPO_Three(Alkyl) (ary
l)), a monoalkylphosphonooxy group (-OPO)_ThreeH
(Alkyl)) and its conjugated base group (hereinafter referred to as alkyl
A phosphonatooxy group), a monoarylphosphono
Xy group (-OPO_ThreeH (aryl)) and its conjugate base
Group (hereinafter referred to as arylphosphonatooxy group),
Group, nitro group, aryl group, alkenyl group, alkynyl
Group. Alkyl in these substituents
Specific examples of the group include the aforementioned alkyl groups.
Specific examples of the reel group include phenyl group and biphenyl.
Group, naphthyl group, tolyl group, xylyl group, mesityl group,
Cumenyl group, fluorophenyl group, chlorophenyl group,
Bromophenyl group, chloromethylphenyl group, hydroxy
Cyphenyl group, methoxyphenyl group, ethoxyphenyl
Group, phenoxyphenyl group, acetoxyphenyl group,
Azoyloxyphenyl group, methylthiophenyl group,
Nylthiophenyl group, methylaminophenyl group, dimethyl
Phenylamino group, acetylaminophenyl group, cal
Boxyphenyl group, methoxycarbonylphenyl group, d
Toxycarbonylphenyl group, phenoxycarbonyl group
Phenyl group, N-phenylcarbamoylphenyl group, phenyl group
Nyl group, nitrophenyl group, cyanophenyl group, sulfo
Phenyl group, sulfonatophenyl group, phosphonophenyl
Group, phosphonatophenyl group and the like.
Examples of the alkenyl group include a vinyl group and 1-pro
Phenyl group, 1-butenyl group, cinnamyl group, 2-chloro
-1-ethenyl group and the like, and examples of the alkynyl group
Ethynyl group, 1-propynyl group, 1-butynyl
Group, trimethylsilylethynyl group, phenylethynyl group
And the like.

As the above-mentioned acyl group (R ⁴ CO--),
Examples of R ⁴ include a hydrogen atom and the above-mentioned alkyl group, aryl group, alkenyl group and alkynyl group. On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to form a divalent organic residue. Can be a straight-chain alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of the preferred substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl group, a methylthiomethyl group, and a trimethylmethyl group. Ruthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group,
Benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Carbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group,
Butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl Group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group,

[0020]

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Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxy Propyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be given.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring, and specific examples include phenyl. Group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group,
And a phenyl group and a naphthyl group are more preferable.

The substituted aryl group is a group in which a substituent is bonded to an aryl group, and a group having a monovalent non-metal atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aryl group is used. To be Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of these substituted aryl groups include a biphenyl group, a tolyl group, a xylyl group,
Mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group,
Methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxy Phenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group,
Allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-
Methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfa Moylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, Phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, -Propenylmethyl group, 2 Butenyl, 2-methyl-allyl phenyl group, 2-methyl propenyl phenyl group, 2-propynyl phenyl group, 2-butynyl phenyl group, 3-butynyl phenyl group, etc. may be mentioned.

Examples of the alkenyl group include those mentioned above. A substituted alkenyl group is a compound in which a substituent is replaced by a hydrogen atom of an alkenyl group and bonded to the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group is the above-mentioned alkenyl group. Can be. Examples of preferred substituted alkenyl groups include

[0025]

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And the like. Examples of the alkynyl group include those described above. The substituted alkynyl group is a substituent in which the hydrogen atom of the alkynyl group is replaced and bonded, and the substituent is the substituent in the above-mentioned substituted alkyl group, while the alkynyl group uses the above-mentioned alkynyl group be able to.

The heterocyclic group means a monovalent group obtained by removing one hydrogen atom on the heterocyclic ring, and one hydrogen atom is further removed from this monovalent group, and the substituent in the above-mentioned substituted alkyl group is bonded to it. The resulting monovalent group (substituted heterocyclic group). Examples of preferred heterocycles include

[0028]

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[0029]

[Chemical 6]

And the like.

As the substituted oxy group (R ⁵ O—), those in which R ⁵ is a monovalent non-metal atomic group excluding hydrogen can be used. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Further, an acyl group (R
The ⁶ CO-), R ⁶ is, can be exemplified alkyl group above, a substituted alkyl group, aryl group or substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy,
Benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, Morpholinopropyloxy, allyloxyethoxyethoxy, phenoxy, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, acetyloxy, benzoyl Examples include an oxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, and a phosphonatoxy group.

As the substituted thio group (R ⁷ S-), those in which R ⁷ is a monovalent non-metal atomic group excluding hydrogen can be used. Preferred examples of the substituted thio group include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be mentioned as shown as the substituted aryl group, R ⁶ acyl group in the acylthio group (R ⁶ CO-) in As described above. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include methylthio, ethylthio, phenylthio, ethoxyethylthio, carboxyethylthio, methoxycarbonylthio, and the like.

Substituted amino group (R ⁸ NH-, (R ⁹ )
The ^{(R 10) N-), R} 8, R 9, R 10 can be used a monovalent nonmetallic radical other than hydrogen. Preferred examples of the substituted amino group include an N-alkylamino group, N, N
-Dialkylamino group, N-arylamino group, N, N
-Diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-
Alkyl ureido group, N ', N'-dialkyl ureide group, N'-aryl ureide group, N', N'-diaryl ureide group, N'-alkyl-N'-aryl ureide group, N-alkyl ureide group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-
Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-
Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N ' -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl —N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, and N-aryl-N-aryloxycarbonylamino group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Substituted alkyl group, and aryl group, it can be exemplified those shown as the substituted aryl group, an acylamino group, N- alkyl acyl amino group, R ⁶ acyl group (R ⁶ CO-) in N- arylacylamino group As described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, and an acetylamino group.

As the substituted carbonyl group (R ¹¹ —CO—), those in which R ¹¹ is a monovalent non-metallic atomic group can be used. Preferred examples of the substituted carbonyl group include a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, N, N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group are exemplified. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-
Examples thereof include a dialkylcarbamoyl group and an N-arylcarbamoyl group, and still more preferable examples include a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of preferred substituents include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-
Examples include a phenylcarbamoyl group, an N, N-diethylcarbamoyl group, and a morpholinocarbonyl group.

As the substituted sulfinyl group (R ¹² —SO—), those in which R ¹² is a monovalent non-metallic atomic group can be used. Preferred examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group. Group, an N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ¹³ —SO ₂ —), one in which R ¹³ is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples of the substituted alkyl group, the aryl group, and the substituted aryl group can be given. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

The sulfonato group (-SO ₃ ^-) are as described above, means a conjugate base anion group of a sulfo group (-SO ₃ H), it is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , C).
a ²⁺ , Zn ^2+, etc.).

The carboxylate group (-CO ₂ ^-) as described above means a conjugate base anion group of a carboxyl group (CO ₂ H), is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (N
a ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means one in which one or two of the hydroxyl groups on the phosphono group are substituted with another organic oxo group, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples thereof include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

[0040] phosphonate group ^{_{(-PO 3 2-, -PO 3 H}} -)
As described above, the phosphono group (—PO ₃ H ₂ ) means a conjugated base anion group derived from the acid first dissociation or the acid second dissociation. Usually it is preferred to use it with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums: aziniums, etc.), and metal ions (Na
⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ and the} like).

The substituted phosphonato group is a conjugated base anion group of one of the above-mentioned substituted phosphono groups in which one hydroxyl group is replaced with an organic oxo group, and specific examples thereof include the above-mentioned monoalkylphosphono group (--PO ₃ H (alkyl)) and a conjugated base of a monoarylphosphono group (—PO ₃ H (aryl)). Usually it is preferred to use it with a counter cation. As such counter cations, those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums,
Iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

Next, R¹And R², R²And R^ThreeAre bound to each other
An example of forming a ring by R ¹And R², R²And R^ThreeBut
The aliphatic ring formed by bonding to each other is a 5-membered ring, 6
A membered ring, a 7-membered ring and an 8-membered aliphatic ring can be mentioned.
And more preferably a 5-membered or 6-membered aliphatic ring.
Can be These are the carbons that make them up
It may have a substituent on the atom (as an example of the substituent
May include the substituents on the above-mentioned substituted alkyl group.
And some of the ring-constituting carbons are heteroatoms (oxygen
Atom, sulfur atom, nitrogen atom, etc.)
Yes. Furthermore, part of this aliphatic ring replaces part of the aromatic ring.
It may be formed.

The oxime ether compound is more preferably an α-substituted keto oxime ether compound represented by the following general formula [II].

[0044]

[Chemical 7]

In the formula, R ² and R ³ are the same or different from each other, and each represents a hydrocarbon group which may have a substituent and which may contain an unsaturated bond, or a heterocyclic group.
R ² and R ³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ are the same or different from each other, and are a hydrogen atom, a hydrocarbon group which may have a substituent and may have an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, It represents a mercapto group, a substituted thio group, an amino group or a substituted amino group. R ¹⁴ and R ¹⁵ are bonded to each other to form a ring,

[0046]

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Represents an alkylene group having 2 to 8 carbon atoms which may be contained in the linking main chain of the ring. R ¹⁶ represents a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group. X
Is a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond,
Hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, carboxylate group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, Phosphonato group, substituted phosphonato group, cyano group,
Alternatively, it represents a nitro group.

The oxime ether compound is more preferably an α-aminoketo oxime ether compound represented by the following general formula [III].

[0049]

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In the formula, R ² , R ³ , R ¹⁴ and R ¹⁵ have the same meanings as described above. R ¹⁷ and R ¹⁸ are the same or different from each other and represent a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated bond. Also, R
¹⁷ and R ¹⁸ are bonded to each other to form a ring,

[0051]

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Represents an alkylene group having 2 to 8 carbon atoms which may contain in the connecting main chain. R ¹⁹ represents a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. Further, the above ketoxime ether is most preferably represented by the following general formula [I
V] is an α-aminoketoxime ether compound.

[0053]

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In the formula, R ² , R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ have the same meanings as described above. Y represents a hydrocarbon linking group which may have a substituent and may contain an unsaturated bond (a divalent group obtained by removing one of hydrogen in the hydrocarbon group). Z has a substituent having an acid group having a pKa in the acid first dissociation of 0 or more and 16 or less, a precursor of the acid group and a conjugated base group of the acid group, or a hydrogen atom which dissociates the acid group. Represents a group substituted with a good hydrocarbon group (referred to as a substituted acid group).

Among these acid groups, precursors, conjugated base groups and substituted acid groups, particularly preferable groups include, for example, the above-mentioned hydroxyl group, substituted oxy group, mercapto group, substituted carbonyl group and carboxylate group, Sulfo group, sulfonato group, sulfamoyl group and its conjugate base group, N-alkylsulfamoyl group and its conjugate base group, N-arylsulfamoyl group and its conjugate base group, N-acylsulfamoyl group and its conjugate Base group,
N-alkylsulfonylsulfamoyl group and its conjugate base group, N-arylsulfonylsulfamoyl group and its conjugate base group, N-alkylsulfonylcarbamoyl group and its conjugate base group, N-arylsulfonylcarbamoyl group and its conjugate base Examples thereof include groups, phosphono groups, substituted phosphono groups, phosphonato groups, substituted phosphonato groups, cyano groups, alkoxysilyl groups, aryloxysilyl groups, hydroxysilyl groups, and conjugate base groups thereof.

Examples of compounds will be shown below, but the invention is not limited thereto. Preferred specific examples of the ketoxime ether compound represented by the general formula [II] are

[0057]

[Chemical 12]

[0058]

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[0059]

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Preferred specific examples of the α-aminoketo oxime ether compound represented by the general formula [III] include:

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

[Chemical 21]

Preferred specific examples of the α-aminoketo oxime ether compound represented by the general formula [IV] include:

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

[Chemical formula 26]

[0074]

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[0075]

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[0076]

[Chemical 29]

[0077]

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[0078]

[Chemical 31]

And the like. General formula [I] or general formula [II] used in the photopolymerizable composition of the present invention,
The oxime ether compound of [III] or [IV] may be used alone or in combination of two or more kinds. The compounds of the general formulas [I] to [IV] are usually 0.05 to 50% by weight, preferably 0.5 to 50% by weight, based on all components of the photopolymerizable composition.
An amount of 35% by weight, more preferably 1 to 25% by weight is used. If this amount is more than 50% by weight, coating film formation failure (cracking) occurs, and if it is less than 0.05% by weight, curing failure becomes unfavorable. Component (iii): A polymer compound having film forming ability will be described.

Examples of the polymer compound having a film-forming ability which is optionally used in the present invention include the following polymers and copolymers. (1) Vinyl polymers: for example, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl methyl ether, polyvinyl chloride, polyethylene and the like, and copolymers thereof. (2) (Meth) acrylic acid ester polymer and alkyl (meth) acrylamide polymer: For example, ethyl poly (meth) acrylate, butyl poly (meth) acrylate, allyl poly (meth) acrylate, poly t-butyl acrylamide, polydi Acetone acrylamide and the like, and copolymers thereof. (3) Unvulcanized rubber: for example, natural rubber, polybutadiene,
Polyisobutylene, polyneoprene, etc., and copolymers thereof. (4) Polyether: For example, polyethylene oxide, polypropylene oxide and the like. (5) Polyamide, copolymer of the following monomers:
For example, caprolactam, laurolactam, hexamethylenediamine, 4,4′-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine, isophoronediamine, diglycols, isophthalic acid, adipic acid, sebacic acid and the like. (6) Polyester: For example, a condensate of terephthalic acid, adipic acid, etc. with ethylene glycol, 1,4-butanediol, etc. (7) Polyurethane: For example, hexamethylene diisocyanate, toluene diisocyanate, naphthalene-1,
Polyurethane of 5-diisocyanate, isophorone diisocyanate, etc. and ethylene glycol, 1,4-butanediol, polyester. Further, isophoronediamine, hexamethylenediamine, or the like may be used as the chain extender.

Further, as the polymer compound capable of forming a film, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in its side chain can be used. It is not limited.
In addition, these may be used alone or in combination. The amount used is 20% by weight to 90% by weight, preferably 30% by weight, based on the total solid content of the photosensitive layer.
It is 80% by weight, more preferably 35% by weight to 70% by weight. Component (iv): Photopolymerization Initiator System Representative examples of the photopolymerization initiator optionally used in the invention include the following, but are not limited thereto.

A) Aromatic Ketones: Preferred examples include "RADIATION CURING IN POLYMER SCIENCE AND TECHNO
LOGY ”JP FOUASSIER, JFRABEK (1993), compounds having a benzophenone skeleton or a thioxanthone skeleton described in p77 to 117, α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, Α-Substituted benzoin compounds described in JP-B-47-22326, JP-B-47-2366
No. 4, a benzoin derivative, JP-A-57-30704
Aroyl phosphonate described in JP-B No. 60-2
Dialkoxybenzophenone described in 6483, Japanese Patent Publication No. 60-26403, benzoin ethers described in JP-A No. 62-81345, Japanese Patent Publication No. 1-34242, U.S. Pat. No. 4,318,791, European Patent 284564A1.
.ALPHA.-Aminobenzophenones described in JP-A-2-21
No. 1452 p-di (dimethylaminobenzoyl)
Benzene, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, acylphosphine described in JP-B-2-9596, thioxanthone described in JP-B-63-61950. And coumarins described in JP-B-59-42864.

B) Aromatic onium salts: V, V of the periodic table
Group I and VII elements, specifically N, P, As, Sb,
Aromatic onium salts of Bi, O, S, Se, Te or I are included. Examples of such aromatic onium salts include JP-B-52-14277 and JP-B-52-1427.
The compounds described in JP-B No. 8 and JP-B No. 52-14279 can be mentioned.

C) Organic peroxide: Almost all organic compounds having one or more oxygen-oxygen bonds in the molecule are included, and examples thereof include methyl ethyl ketone peroxide, benzoyl peroxide, and t-butyl hydroperoxide. Examples thereof include oxide, cumene hydroperoxide, t-butylperoxyoctanoate, di-t-butyldiperoxyisophthalate.

D) Thio compound: the following general formula [V]

[0086]

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(In the formula, R ²⁰ represents an alkyl group, an aryl group or a substituted aryl group, R ²¹ represents a hydrogen atom or an alkyl group, and R ²⁰ and R ²¹ are bonded to each other to form an oxygen atom;
The non-metal atomic group necessary for forming a 5-membered to 7-membered ring which may contain a hetero atom selected from sulfur and nitrogen atoms is shown. ) E) Hexaarylbiimidazole: JP-B-45-37
377 and Japanese Patent Publication No. 44-86516, for example, the lophine dimers, for example, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5' tetraphenylbiimidazole, 2,2'-bis ( o-trifluoromethylphenyl) -4,4 ′, 5,5 ′ tetraphenylbiimidazole and the like.

F) Ketoxime esters: eg 3-
Benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one 2-acetoxyimino-1-
Examples thereof include phenylpropan-1-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. g) Borate salts: compounds described in U.S. Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, 109,773 and the like can be mentioned.

H) Azonium salt compound: JP-A-63-1
38345, JP-A-63-142345, JP-A-6-
Examples thereof include compounds described in JP-A-3-142346, JP-A-63-143537, and JP-B-46-42363. i) Metallocene compounds: JP-A-59-152396,
JP-A-61-151197, JP-A-63-41484
And the iron-arene complex described in JP-A-1-304453, and the like.

J) Active ester compound: Japanese Patent Publication No. 62-6
No. 223, an imide sulfonate compound, JP-B-63
No. 14340, active sulfonates described in JP-A No. 59-174831, and the like. k) Compounds having a carbon-halogen bond: Wakabayashi et al., Bul
l. Chem. Soc. Japan, 42, 2924 (1969), compounds described in U.S. Pat. No. 1,388,492, compounds described in JP-A-53-133428, German Patent 3,33.
7,024, J. Or by FC Schaefer and others
g. Chem. 29, 1527 (1964), the compounds described in JP-A-62-58241, JP-A 5-28
Compounds described in 1728, German Patent 2,641,100
German patent 3,333,450 German patent 3,02
Examples thereof include compounds described in No. 1,590 and German Patent No. 3,021,599.

Of these, preferred examples are a)
Aromatic ketones, c) organic peroxides, e) hexaarylbiimidazole compounds, i) metallocene compounds, k)
Compounds having a carbon-halogen bond can be mentioned,
More preferred are a) aromatic ketones and k) compounds having a carbon-halogen bond. In the present invention, the above compounds may be used alone or in combination of two or more kinds.

Further, in the photopolymerization initiation system of the present invention, it is preferable that a known branch sensitizing dye or dye is allowed to coexist. Examples of preferable spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene, etc.), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal, etc.), cyanines ( For example, thiacarbocyanine, oxycarbocyanine, etc., merocyanines (for example, merocyanine, carbomerocyanine, etc.), thiazines (for example, thionine, methylene blue, toluidine blue, etc.), acridines (for example, acridine orange, chloroflavin, acrylin). Flavins), phthalocyanines (eg, phthalocyanines, metal phthalocyanines, etc.), porphyrins (eg, tetraphenylporphyrin, metalporphyrins, etc.), chlorophylls (eg, chlorophyll, chlorophyllin). Down, central metal-substituted chlorophyll), anthraquinones (e.g., anthraquinone), squaliums (for example, squarylium and the like) and the like.

More preferably, Japanese Patent Publication No. 37-13034
Styryl dyes described in JP-A-62-143044, cation dyes described in JP-A-62-143044, quinoxalinium salts described in JP-B-59-24147, new methylene blue compounds described in JP-A-64-33101, and JP-A-64-59767. Anthraquinones described in JP-A No. 2-1714, benzoxanthenes described in JP-A No. 2-1714, JP-A No. 22614/1990, and JP-A No.
No. 226149, acridines, Japanese Examined Patent Publication No. 40-2
Pyrylium salts described in 8499, Japanese Examined Patent Publication No. 46-423
No. 63, cyanines, benzofuran dyes described in JP-A-2-63053, conjugated ketone dyes described in JP-A-2-85858, JP-A-2-216154, JP-A-57.
No. 10605, Azocinnamylidene derivatives described in JP-B No. 2-30321, JP-A-1-28710.
Cyanine dyes described in JP-A No. 62-31844,
JP-A-62-31848, JP-A-62-143043
Xanthene dyes described in JP-B No. 59-28325, amino styryl ketones described in JP-B No. 59-28325, and JP-B No. 61-9621.
JP-A-2-179643, JP-A-2-24405
No. 0, JP-B-59-28326, JP-A-59-893.
No. 03, Japanese Patent Application No. 6-269047, and other merocyanine dyes. More preferable examples are described in Japanese Patent Publication No. 61-9621, Japanese Patent Publication No. 2-179643, Japanese Patent Publication No. 2244050, Japanese Patent Publication No. 59-28623, Japanese Patent Publication No. 59-89303, and Japanese Patent Application No. 6-269047. The merocyanine dyes of These are preferably used alone or in combination of two or more.

Further, a known compound having a function of further improving the sensitivity of the photopolymerizable photosensitive layer of the present invention or suppressing the inhibition of polymerization by oxygen may be added as a cosensitizer. Examples of such co-sensitizers include amines such as "Journal of Polymer Society" by MR Sander et al.
Vol. 10, pp. 3173 (1972), Japanese Patent Publication No. 44-201
89, JP-A-51-82102, JP-A-52-13.
4692, JP-A-59-138205, JP-A-60
-84305, JP-A-62-18537, JP-A-SHO-6
4-33104, the compound of Resarch Disclosure 33825, etc. are mentioned.

Other examples of the co-sensitizer include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806 and JP-A-5-142772, and JP-A-56. The disulfide compound of No. 75643 and the like can be mentioned. As other examples, amino acid compounds (for example, N-phenylglycine, etc.), organometallic compounds described in JP-B-48-42965, hydrogen donors described in JP-B-55-34414, and Japanese Patent Application No. 5-91.
No. 089, sulfur compound, Japanese Patent Application No. 5-32147, phosphorus compound, Japanese Patent Application No. 6-191605, S
Examples thereof include i-H and Ge-H compounds.

The ratio of the component ii) to the component iv) used in the present invention is the ratio of the component i to 1 part by weight of the oxime ether of ii).
It is suitable to use 0.01 to 50 parts by weight of v), more preferably 0.05 to 20 parts by weight, and most preferably 0.1 to 10 parts by weight. Other components will be described. In addition to the above, it is preferable to further add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, 4,4′-thiobis (3 −
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol),
2-Mercaptobenzimidazole and the like are useful, and in some cases, a dye or pigment and a pH indicator or leuco dye as a printing agent can be added for the purpose of coloring the photosensitive layer. A silicone-based surfactant or a fluorine-based surfactant may be added to improve coatability. Further, a diazo resin may be added to improve the adhesion between the photosensitive layer and the primer layer. In addition, in order to improve the adhesion between the silicone rubber layer and the photosensitive layer, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane in the photosensitive layer,
Silicone compounds such as polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate may be added.
In addition, a plasticizer for imparting flexibility to the coating film (for example, polyethylene glycol, tricresyl phosphate, etc.),
Stabilizers (eg phosphoric acid etc.) may be added. The amount of these additives added is usually 10% by weight or less based on the total composition of the photosensitive layer. In some cases, the hydrophobic silica powder treated with the (meth) acryloyl group- or allyl group-containing silane coupling agent may be added in an amount of 50% by weight or less based on the total photosensitive layer composition.

The above-mentioned photosensitive layer composition used in the present invention is, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, ethanol, methyl ethyl ketone,
A suitable solvent such as N, N-dimethylacetamide or toluene is dissolved alone or in a mixed solvent thereof, and the solution is coated on a support. The coating weight is 0.1 to 2 after drying.
The range of 0 g / m ² is suitable, and preferably 0.5 to 1
It is in the range of 0 g / m ² .

The silicone rubber layer used in the present invention is usually a crosslinked silicone rubber layer,
It is a film formed by curing the following composition A or B. Composition A (a) Diorganopolysiloxane (having a number average molecular weight of 3,000 to 40,000) 100 parts by weight (b) Condensation type crosslinking agent 3 to 70 parts by weight (c) Catalyst 0.01 to 40 parts by weight The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following general formula, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms, a vinyl group or an aryl group, and May have an appropriate substituent. Generally 60% of R ¹ and R ²
The above are preferably a methyl group, a vinyl halide group, a halogenated phenyl group, or the like.

[0099]

[Chemical 33]

It is preferable to use a diorganopolysiloxane having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 4
50,000, more preferably 5,000 to 3
6,000. The component (b) may be any condensation type, but is preferably one represented by the following general formula.

R ¹ m · Si · Xn (m + n = 4, n is 2 or more) Here, R ¹ has the same meaning as the above R ^1, and X is a substituent as shown below. Cl, Br, halogen H, such as ^{I, OH, OCOR 3, OR} 3, -O-N = C
(R ⁴⁾ (R ⁵⁾ or -N (R ⁴⁾ (R ⁵⁾ organic substituent such as.

Here, R ³ is an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and R ⁴ and R ⁵ are alkyl groups having 1 to 10 carbon atoms. Component (c) includes metal carboxylates such as tin, zinc, lead, calcium and manganese, for example, dibutyl laurate, lead octylate, lead naphthenate, etc., or known catalysts such as chloroplatinic acid, etc. .

Composition B (d) Diorganopolysiloxane having an addition-reactive functional group, number average molecular weight of 3,000 to 40,000 100 parts by weight (e) Organohydrogenpolysiloxane 0.1 to 10 parts by weight (F) Addition catalyst 0.00001 to 1 part by weight The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an alkenyl group directly bonded to a silicon atom in one molecule (more preferably a vinyl group). ), The alkenyl group may be at the molecular weight end or in the middle, and the organic group other than the alkenyl group may be substituted or non-substituted. Substituted carbon number 1 to 1
0 is an alkyl group or an aryl group. Also, component (d)
May have a trace amount of hydroxyl groups. Further, the component (d) has a number average molecular weight of 3,000 to 40,000, and more preferably 5,000 to 36,000.

As the component (e), polydimethylsiloxane having both terminal hydrogen groups, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having both terminal methyl groups, cyclic polymethylsiloxane, both Examples include polymethylsiloxane having a terminal trimethylsilyl group, dimethylsiloxane having both terminal trimethylsilyl groups (methylsiloxane) copolymer, and the like.

The component (f) is arbitrarily selected from known ones, but a platinum-based compound is particularly preferable, and platinum simple substance, platinum chloride, chloroplatinic acid, olefin coordinated platinum and the like are exemplified. In order to control the curing rate of these compositions, organopolysiloxanes containing vinyl groups such as tetracyclo (methylvinyl) siloxane, alcohols containing carbon-carbon triple bonds, acetone, methyl ethyl ketone, methanol, ethanol, It is also possible to add a crosslinking inhibitor such as propylene glycol monomethyl ether.

In the silicone rubber layer, if necessary, fine powder of an inorganic material such as silica, calcium carbonate, titanium oxide, a silane coupling agent, an adhesion aid such as a titanate coupling agent or an aluminum coupling agent. Alternatively, a photopolymerization initiator may be added. The silicone rubber layer in the present invention has a problem that the ink repelling property is reduced when the thickness is small and scratches are likely to occur, and when the thickness is large, the developability is deteriorated, so that the thickness is 0. .
5 to 5 g / m ² is preferable, and more preferably 1 to 3 g / m ^2.
m ² .

In the waterless planographic printing plate described here, various silicone rubber layers may be further coated on the silicone rubber layer. In addition, an adhesive layer is provided between the photosensitive layer and the silicone rubber layer for the purpose of increasing the adhesive force between the photosensitive layer and the silicone rubber layer or preventing poisoning of the catalyst in the silicone rubber layer composition. May be. Furthermore,
To protect the surface of the silicone rubber layer, a transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, or cellophane is laminated on the silicone rubber layer, or a polymer coating is applied. May be. These films may be used after being stretched. Further, the surface may be matted, but the one without matting is preferable in the present invention.

The light sources for imagewise exposure of the waterless lithographic printing plate thus obtained include ultrahigh pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible light and ultraviolet light. Various laser lamps, fluorescent lamps, tungsten lamps, etc. can be used. As the developing solution used in the present invention, known developing solutions for waterless lithographic printing plates can be used, but from the viewpoint of safety, water or an aqueous solution of a water-soluble organic solvent containing water as a main component is preferable. In consideration of safety and flammability, the concentration of the water-soluble solvent is preferably less than 40% by weight. Known compounds include, for example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G" (manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.). ) Or a halogenated hydrocarbon (trichlene, etc.) to which the following polar solvent is added, or the polar solvent itself: alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether Ether, polypropylene glycol, tetraethylene glycol, etc.) Ketones (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methyl lactate, butyl lactate,
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.) Others (triethyl phosphate, tricresyl phosphate, etc.) Also, water can be added to the organic solvent-based developer or the organic solvent can be added to water by using a surfactant or the like. Melted ones,
Further, an alkaline agent (for example, sodium carbonate, diethanolamine, sodium hydroxide, etc.) added thereto, or simply water (tap water, pure water, distilled water, etc.) and the like can be mentioned.

Further, dyes such as crystal violet, Victoria pure blue, and Astrazone red can be added to the developing solution to dye the image area simultaneously with the development. The development can be performed by a known method such as rubbing the plate surface with a developing vat containing the above-mentioned developing solution or pouring the developing solution onto the plate surface and then rubbing with a developing brush in water. The temperature of the developing solution can be developed at any temperature, but is preferably 10 ° C to 50 ° C. As a result, the ink repellent layer in the image area is removed, and that area becomes the ink receiving area.

In the printing plate thus obtained, the exposed image portion can be dyed with a dyeing solution so as to be detected in order to confirm its image forming property. When the developer does not contain a dye for dyeing the exposed image area, it is treated with a dyeing solution after development. By soaking the dyeing solution in a soft pad and rubbing the image area lightly, only the exposed image area of the photosensitive layer is dyed, whereby it can be confirmed that the development is sufficiently performed up to the highlight area. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes can be used alone or in a mixture of two or more of water, alcohols, ketones and ethers. What is dissolved or dispersed is used. In order to improve the dyeability, carboxylic acids, amines, surfactants,
It is also effective to add a dyeing aid, an antifoaming agent and the like.

The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the stickiness of the plate surface can be suppressed and the handleability of the printing plate can be improved. Further, when the printing plates thus treated are stacked and stored, it is preferable to insert and sandwich a slip sheet for protecting the printing plates.

It is preferable that the above-mentioned developing treatment and dyeing treatment, or subsequent washing and drying treatments are carried out by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-220061.

[0113]

The waterless lithographic printing plate of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet rays to visible rays.

[0114]

[Examples 1 to 8 and Comparative Examples 1 to 3]

(Preparation of support) A rolled aluminum plate having a thickness of 0.24 mm is first treated with a 10% by weight sodium hydroxide aqueous solution to give 50 parts.
After dipping at 60 ° C. for 60 seconds for cleaning treatment, it was washed with water and then neutralized with 20% by weight nitric acid. After washing with water, in a 0.7 wt% nitric acid aqueous solution, a rectangular wave alternating waveform having a voltage of 13 V for the anode and a voltage of 6 V for the cathode was used (JP-A-52-77).
(Power supply waveform described in the example of Japanese Patent Publication No. 702) electrochemically grained for 20 seconds. Then, the amount of etching was 2.5 g /
The treatment time was adjusted so as to be m ^2, and then the resultant was washed with water and neutralized with 20% by weight nitric acid. 18% by weight after washing with water
Anodize the solution in a sulfuric acid aqueous solution at a current density of 1.5 A / dm ² at 25 ° C so that the amount of oxide film is 1.7 g / m ² , then rinse with water, immerse in 2% by weight sodium silicate aqueous solution at 70 ° C for 1 minute, and rinse with water. Then, it was dried to obtain a support. The average roughness of the obtained support was 0.4 μm (Ra indication). (Coating of primer layer) Dry weight on support 3 g / m
As it will be ^2, coated with a primer layer below, 130
The mixture was heated at ℃ for 2 minutes and dried.

Polyurethane resin (isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropan-1,3-diol) / isophoronediamine) 10 parts by weight p-diazodiphenylamine and para Hexafluorophosphate of polycondensation product with formaldehyde 0.1 part by weight MCF323 (Dainippon Ink and Chemicals, Inc., surfactant) 0.03 part by weight Propylene glycol methyl ether acetate 50 parts by weight Lactic acid Methyl 20 parts by weight ・ Pure water 1 part by weight After that, Nuark FT261V UDNS ULTRA-PLUS FLIPTO
20 count exposure was performed using a P PLATE MAKER vacuum exposure machine. Coating of photosensitive layer) A photopolymerizable photosensitive liquid having the following composition was coated on the primer layer so that the dry weight was 3 g / m ^2, and 1
It was dried at 00 ° C for 1 minute.

Polyurethane resin (isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropan-1,3-diol) / isophoronediamine) 1.5 parts by weight Sartomer 9035 (Sartomer) Acrylate monomer made by the company) 0.3 part by weight Xylylenediamine 1 mol / glycidyl methacrylate 4 mol adduct (polyfunctional monomer) 1.2 parts by weight Polyethylene glycol 400 (Wako Pure Chemical Industries, Ltd.) 0.05 Parts by weight-photopolymerization initiator system shown in Table-1 MCF323 (Dainippon Ink and Chemicals, Inc., surfactant) 0.03 parts by weight-methyl ethyl ketone 10 parts by weight-propylene glycol monomethyl ether 25 parts by weight (silicone Application of rubber layer (ink repellent layer)) Above On the polymerizable photosensitive layer was coated so that the silicone rubber composition solution having the following dry weight ^{2g / m 2, 140 ℃,} 2
Dried for minutes.

Α, ω-divinylpolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight (CH3) 3-Si-O- (SiH (CH3) -O) 8-Si (CH3) 3 0.5 part by weight Parts-polydimethylsiloxane (polymerization degree of about 8,000) 0.5 parts by weight-olefin-chloroplatinic acid 0.2 parts by weight-inhibitor (CH CC (CH3) 2Si (CH3) 3) 0.3 parts by weight- Isopar G (manufactured by Esso Chemical Co., Ltd.) 140 parts by weight A 6 μm thick polyethylene terephthalate film was laminated on the surface of the silicone rubber layer obtained as described above to obtain a waterless planographic printing plate.

The photosensitivity test was conducted with visible light. As the visible light, monochromatic light obtained through a Kenko optical filter BP-49 using a xenon lamp as a light source was used. For the photosensitivity measurement, a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet having a transmission optical density of 0.05 at the first step and increasing by 0.15 sequentially up to 15 steps) was used. The number of clear steps of the PS step guide when the illuminance of the photosensitive film surface is 0.0132 mW / cm2 for 15 seconds.
The number of steps in which the silicone rubber layer is completely left is shown.
The larger this number is, the higher the sensitivity is.

Then, the laminate film was peeled off by heating at 100 ° C. for 1 minute, and the following developing treatment was immediately carried out. (Development Treatment) The plate was immersed in warm water at 40 ° C. and rubbed with a development pad to remove the silicone rubber layer in the unexposed area. Subsequently, it was dyed with a dyeing solution having the following composition, and the sensitivity was evaluated.

(Staining liquid) -Crystal violet 0.1 part by weight-Diethylene glycol monoethyl ether 15 parts by weight-Pure water 85 parts by weight

[0121]

[Table 1]

As is clear from Table 1, the waterless lithographic printing plate containing the oxime ether compound of the present invention has higher sensitivity than the one containing no oxime ether compound. [Examples 9 to 15 and Comparative Examples 4 to 5] (Coating of Photosensitive Layer) A photopolymerizable photosensitive liquid having the following composition was dried on a primer layer prepared in the same manner as in Examples 1 to 8 to give a dry weight of 3 g / m. ^It was applied so as to be ^2, and dried at 100 ° C. for 1 minute.

Polyurethane resin (isophorone diisocyanate / polyester (adipic acid / 1,4-butanediol / 2,2-dimethylpropan-1,3-diol) / isophoronediamine 1.5 parts by weight pentaerythritol tetraacrylate 0 .3 parts by weight-Xylylenediamine 1 mol / glycidyl methacrylate 4 mol adduct (polyfunctional monomer) 1.2 parts by weight-Photoinitiator system shown in Table 2-MCF323 (Dainippon Ink and Chemicals, Inc.) Manufacture, surfactant) 0.03 parts by weight Methyl ethyl ketone 10 parts by weight Propylene glycol monomethyl ether 25 parts by weight (application of silicone rubber layer (ink repellent layer)) The following silicone rubber composition on the photopolymerizable photosensitive layer liquid was coated so that the dry weight ^{2g / m 2, 140 ℃,} 2
Dried for minutes.

9 parts by weight of polydimethylsiloxane having hydroxyl groups at both ends (polymerization degree of about 700) 0.3 parts by weight of methyltriacetoxysilane 0.3 parts by weight of trimethoxysilylpropyl-3,5-diallyl isocyanurate Dibutyltin dioctanoate 0.03 parts by weight Isopar G (manufactured by Esso Chemical Co., Ltd.) 160 parts by weight A 6 μm thick polyethylene terephthalate film is laminated on the surface of the silicone rubber layer obtained as described above, and water is added. A lithographic printing plate was obtained. After exposure was performed in the same manner as in Examples 1 to 8, heating was carried out at 100 ° C. for 1 minute, the laminate film was peeled off, and the following developing treatment was immediately carried out.

(Development treatment) After immersing the plate in polypropylene glycol at 35 ° C for 30 seconds, the plate was rubbed with a developing pad while being washed with water to remove the silicone rubber layer in the unexposed area. Then, dye with a dyeing solution of the following composition,
The sensitivity was evaluated. (Staining solution) -Crystal violet 0.1 part by weight-Diethylene glycol monoethyl ether 15 parts by weight-Pure water 85 parts by weight

[0126]

[Table 2]

As is clear from Table 2, the waterless lithographic printing plate containing the oxime ether compound of the present invention has a higher sensitivity than that containing no oxime ether compound.

Claims (1)

[Claims] 1. A primer layer, a photopolymerizable photosensitive layer and a silicone rubber layer are laminated in this order on a support, and the photopolymerizable photosensitive layer contains the following components i) and ii). A photosensitive lithographic printing plate that does not require fountain solution. i) photopolymerizable ethylenically unsaturated group-containing compound ii) oxime ether compound