JP2002221788A - Original plate for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly-sensitive original plate for a planographic printing plate excelling in printing/work-up resistance and containing a photo radical polymerized composition-based photosensitive layer, especially enabling plate making directly from digital data of computer, etc., recorded by using a solid- state laser or a laser diode emitting ultraviolet, visible or infrared radiations. SOLUTION: The highly-sensitive original plate for the planographic printing plate is provided with a compound containing two or more chemical structures expressed by the following general formula (I) per molecule. (where: R1 represents H or an alkyl group of 1-5 carbon numbers, and R2 represents an alicyclic ring of 6 carbon numbers or an aromatic ring residue).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor capable of making a plate directly from digital signals of a computer or the like by using various lasers.

[0002]

2. Description of the Related Art Solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm can be easily obtained with high output and small size. Is very useful as a recording light source when making a plate directly from digital data of a computer or the like. Various studies have been made on recording materials sensitive to these various laser beams. As a typical example, first, as a material recordable with an infrared laser having a photosensitive wavelength of 760 nm or more, US Pat. No. 4,708,892.
No. 5, the positive-type recording material described in JP-A-8-276558, and the acid-catalyzed cross-linkable negative-type recording material described in JP-A-8-276558.
Secondly, as a recording material compatible with ultraviolet or visible light laser of 300 nm to 700 nm, US Pat.
There are a large number of radical polymerization type negative recording materials described in No. 5 and Japanese Patent Publication No. 44-20189. Usually, the photo-radical polymerization system has high sensitivity, but one having higher printing durability has been demanded.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lithographic printing plate precursor having a photosensitive layer using a photo-radical polymerization composition, which is considered to be the most sensitive and promising among image forming techniques. High-sensitivity, excellent in printing durability and stain resistance, especially by recording using a solid-state laser and a semiconductor laser beam that emit ultraviolet light, visible light and infrared light, and so on. Is to provide a lithographic printing plate precursor that can be directly made from digital data.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in a lithographic printing plate precursor having a photopolymerizable photosensitive layer, the photosensitive layer contains a specific imide acrylate monomer to achieve the above object. Was achieved. That is, the present invention has the following configuration. A lithographic printing plate precursor having a photopolymerizable photosensitive layer containing a compound having two or more structures represented by the following general formula (I) in one molecule.

[0005]

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(R ₁ represents H or an alkyl group having 1 to 5 carbon atoms, and R ₂ represents an alicyclic or aromatic ring residue having 6 carbon atoms.) The lithographic printing plate precursor of the present invention is prepared by photopolymerization. It is considered that the chemical properties of the polymerizable compound contained in the photosensitive layer, such as the cyclic structure represented by the general formula (I), make the sensitivity, printing durability, and stain resistance excellent. .

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION <Compound Having Structure Represented by General Formula (I) in the Present Invention> The characteristic compound of the present invention is represented by the general formula (I) contained in a photopolymerizable photosensitive layer. (Imide acrylate monomer) having two or more structures in one molecule. Examples of the compound having two or more structures represented by the general formula (I) in one molecule include:
Although not particularly limited, those having the following structures are exemplified.

[0008]

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The compound of the present invention is most preferably a compound having both the structure represented by the general formula (I) and another radically polymerizable group in the molecule and making a polyfunctional contribution to substantial photopolymerization. .

In the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the present invention, as the compound having an ethylenically unsaturated bond capable of addition polymerization, a compound having the structure represented by the above general formula (I) alone or a compound thereof may be used. A mixture of two or more kinds or a mixture with a conventionally known addition-polymerizable compound having an ethylenically unsaturated bond described below is used. Examples of conventionally known compounds having an addition-polymerizable ethylenically unsaturated bond include, for example, unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric acids. Examples thereof include esters with a polyhydric alcohol compound, and amides of the above unsaturated carboxylic acid with an aliphatic polyamine compound.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate Acrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, SO Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3 -Methacryloxy-2-h Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (acryloxy ethoxy)
Phenyl] dimethylmethane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexane. Examples include methylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

As another example, see Japanese Patent Publication No. 48-417.
JP-A-08-208, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. Vinyl urethane compounds containing the above polymerizable vinyl groups are exemplified.

CH ₂ ＣC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ )

Also, urethane acrylates as described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-30490, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and the like. Furthermore, the Journal of the Adhesion Society of Japan vol.20, No. 7, 300-308 (1984) as photocurable monomers and oligomers can also be used. In the present invention, these monomers may be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. In the present invention, among these, combination use with a urethane acrylate monomer is preferable.

The amount of all the polymerizable group-containing compounds, including the compound having the structure represented by the general formula (I), is usually 1 to 99.99 based on the weight of all components of the photopolymerizable photosensitive layer.
%, Preferably 5 to 90.0%, more preferably 10 to 70%
% Amounts are used. (The percentages here are weight percentages). However, the content of the compound of the general formula (I) of the present invention contained in all the polymerizable group-containing compounds is 0.005 to 100.
% By weight, preferably 1% to 100% by weight, more preferably 30% to 100% by weight. If the amount is less than 0.005, the effect of the present invention may not be exhibited.

Next, the photopolymerization initiator used in the photopolymerizable photosensitive layer of the lithographic printing plate precursor according to the present invention will be described. Preferred photopolymerization initiators include (a) aromatic ketones,
(B) an aromatic onium salt compound, (c) an organic peroxide,
(D) a thio compound, (e) a hexaarylbiimidazole compound, (f) a ketoxime ester compound, (g)
Examples include borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, and (k) compounds having a carbon-halogen bond. (A) Preferable examples of aromatic ketones include “RADIAT
ION CURING IN POLYMERSCIENCE AND TECHNOLOGY''JPF
OUASSIER JFRABEK (1993), a compound having a benzophenone skeleton or a thioxanthone skeleton according to p77 to 117,
For example

[0019]

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[0020]

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[0021]

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And the like. More preferred examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416 and JP-B-47-3981.
The benzoin ether compound described, for example,

[0023]

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Α-Substituted benzoin compounds described in JP-B-47-22326, for example,

[0025]

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Benzoin derivatives described in JP-B-47-23664, aroylphosphonic esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example,

[0027]

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JP-B-60-26403, JP-A-62-8
Benzoin ethers described in 1345, for example,

[0029]

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Japanese Patent Publication No. 1-34242, US Patent No. 4,3
18,791 and α-aminobenzophenones described in EP 0284561A1, for example,

[0031]

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P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-21452, for example,

[0033]

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Thio-substituted aromatic ketones described in JP-A-61-194062, for example,

[0035]

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The acylphosphine sulfide described in JP-B-2-9597, for example,

[0037]

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Acylphosphines described in JP-B-2-9596, for example,

[0039]

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Thioxanthones described in JP-B-63-61950 and coumarins described in JP-B-59-42864 can be exemplified. Further, as another example of (b) an aromatic onium salt, an element of Groups V, VI and VII of the periodic table, specifically, N, P, As, Sb, Bi, O,
Includes aromatic onium salts of S, Se, Te, or I. Examples of such aromatic onium salts include the compounds disclosed in JP-B-52-14277, JP-B-52-14278, and JP-B-52-14279. In particular,

[0041]

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[0042]

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[0043]

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[0044]

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The following can be mentioned. Further, the following diazonium salts can be mentioned.

[0046]

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[0047]

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Another example of the photopolymerization initiator used in the present invention, (c) “organic peroxide” includes oxygen-
Almost all organic compounds having one or more oxygen bonds are included, and examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide,
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (Tertiary butyl peroxide) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5
-Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butylperoxyisopropyl) benzene, 2,5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-xanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide , Diisopropyl peroxydicarbonate, di-
2-ethylhexyl peroxydicarbonate, di-2
Ethoxyethyl peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate,
Tertiary butyl peroxy acetate, tertiary butyl peroxy pivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy octanoate, tertiary butyl peroxy-
3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4 '
-Tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

Among them, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4
Peroxide esters such as 4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate Systems are preferred.

The thio compound (d) as a photopolymerization initiator used in the present invention is represented by the following general formula [II].

[0051]

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(Where 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 oxygen, sulfur and The group of nonmetallic atoms necessary for forming a 5- to 7-membered ring which may contain a hetero atom selected from a nitrogen atom is shown below.) The alkyl group in the above general formula [II] has 1 to 1 carbon atoms. Four are preferred. The aryl group is preferably a group having 6 to 10 carbon atoms such as phenyl and naphthyl. The substituted aryl group is preferably a halogen atom such as a chlorine atom and an alkyl group such as a methyl group. And those substituted with an alkoxy group such as a methoxy group or an ethoxy group. R ²¹ is
Preferably, it is an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula [II] include the following compounds.

[0053]

[Table 1]

As another example of the photopolymerization initiator used in the present invention, (e) hexaarylbiimidazole includes:
Lophin dimers described in JP-B-45-37377 and JP-B-44-86516, for example, 2,2'-bis (o
-Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 '-Bis (o, p-dichlorophenyl)
-4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-
And tetraphenylbiimidazole.

Other examples of the photopolymerization initiator used in the present invention, (f) ketoxime esters include 3-benzoyloximinobutan-2-one, 3-acetoxyiminobutan-2-one, -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-
ON, 2-acetoxyimino-1-phenylpropane-
1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like Is mentioned. Examples of the borate salt (g), which is another example of the photopolymerization initiator in the present invention, include a compound represented by the following general formula [III].

[0056]

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(Where R ²² , R ²³ , R ²⁴ and R
²⁵ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ are
Two or more groups may combine to form a cyclic structure. However, at least one of R ²² , R ²³ , R ²⁴ and R ²⁵
One is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation). The alkyl group of R ^{22 to} R ²⁵ includes linear, branched and cyclic alkyl groups, and preferably has 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As the substituted alkyl group, a halogen atom (for example, -Cl, -Br or the like), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group,

[0058]

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(Where R²⁶, R²⁷Is independently a hydrogen atom,
Represents an alkyl group having 1 to 14 carbon atoms or an aryl group
You. ), -COOR²⁸(Where R²⁸Is hydrogen atom, carbon number
1 to 14 alkyl groups or aryl groups. ),-
OCOR²⁹Or -OR³⁰(Where R ²⁹, R³⁰Is 1 carbon
And 14 to 14 alkyl groups or aryl groups. Replace)
Those having as a group are included. R above^{twenty two}~ R^{twenty five}Ants
Examples of the phenyl group include a phenyl group and a naphthyl group.
And a substituted aryl group as described above.
The substituent of the above-mentioned substituted alkyl group is substituted for the aryl group as described above.
Or, those having an alkyl group having 1 to 14 carbon atoms are included.
It is. R above^{twenty two}~ R^{twenty five}The alkenyl group of
2-18 linear, branched and cyclic ones are included. Substitution al
Examples of the substituent of the kenyl group include the above-mentioned substituted alkyl group.
Those included as the substituents are included. R above^{twenty two}~ R^{twenty five}No
As the rukinyl group, a linear or branched C2-28 carbon atom
And the substituent of the substituted alkynyl group is
The substituents of the substituted alkyl group include those mentioned above.
You. In addition, the above R^{twenty two}~ R^{twenty five}N, S and heterocyclic groups as
Or a ring having at least one of O and O, preferably
A 5- to 7-membered heterocyclic group may be mentioned.
A ring may be contained. Further, as a substituent,
Even if it has one of the substituents of the substituted aryl group
Good. Specific examples of the compound represented by the general formula [III] include
U.S. Pat. Nos. 3,567,453 and 4,343,8
No. 91, European Patent Nos. 109,772 and 109,772.
No. 773 and the compounds shown below
Is mentioned.

[0060]

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Examples of (h) azinium salt compounds which are other examples of the photopolymerization initiator of the present invention are described in
Nos. 138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143535, and JP-B-46-42363.

Another example of the photopolymerization initiator (i) of the metallocene compound is described in JP-A-59-152396.
JP-A-61-151197, JP-A-63-414
No. 84, JP-A-2-249, JP-A-2-4705 and the titanocene compounds described in JP-A-1-30445.
No. 3 and JP-A-1-152109.

Specific examples of the titanocene compound include:
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-
Cyclopentadienyl-Ti-bis-2,3,4,5
6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-T
i-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-T
i-bis-2,4-difluorophenyl-1-yl, di-
Methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5
6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3 -(Pyri-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbiaroyl-
Amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetylamino) phenyl] titanium, bis (cyclopentadi Enil)
Bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (2,2-dimethylbuta Noyl) amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-butyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
Pentyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,
2-dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-methylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylisobutyrylamino) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3-
(N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (2,2,5,5-tetramethyl-1,2,5-azadisirolidin-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-3- (4-dodecylphenylsulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (4- (1-pentylheptyl)
Phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (ethylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamide)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( Hexadecylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl) sulfonylamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamide)] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (pyrrolidine-
2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (3,4-dimethyl-3-pyrrolidin-2,5-dion-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phthalimido) phenyl] titanium , Bis (cyclopentadienyl) bis [2,6-difluoro-3-isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((2
-Chloroethoxy) -carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (phenoxycarbonylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (3-butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylureido) phenyl] titanium, bis ( Cyclopentadienyl) bis [2,6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N, N-diacetylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,3-dimethylureido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (octadecanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 6-difluoro-
3- (2-ethylhexanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) Screw [2
6-difluoro-3- (pivaloylamino) phenyl]
Titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethyl-2)
-Methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentane Dienyl) bis [2,6-difluoro-3- (3-phenylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(2-chloromethyl-2-methyl-3-chloropropanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (3,4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-ethylbenzoylamino) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(Benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(3-phenylpropyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3-ethylheptyl)-
2,2-dimethylpentanoylamino] phenyltitanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadi Enil)
Bis [2,6-difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolan-2-ylmethyl) benzoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (3-ethylheptyl)-
2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-toluyl) amino) phenyl] titanium, Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-
(Oxolani-2-ylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluylmethyl) benzoylamino) phenyl] Titanium,

Bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (4-toluylmethyl)-
(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) ) Screw [2
6-difluoro-3- (N-hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,
4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4-dimethylpentyl) -2,2-dimethyl Pentanoylamino)
Phenyl) titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (2,2-
Dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (2,2-dimethyl-3-allyloxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-allylacetylamino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl) Methylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethyl-
(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N- (2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) Bis [2,6-difluoro-3- (N- (3-
Phenylpropyl) -2,2-dimethylpentanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-cyclohexylmethyl-2,2-dimethylpentanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (2-ethylhexyl)-
2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N- (3-phenylpropyl) pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-butyl-2,2-dimethylpentanoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-benzyl- (4
-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(2-methoxyethyl)-(4-toluyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-cyclohexylmethyl-
(2-ethyl-2-methylheptanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (2-ethyl- 2-methylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethylpentanoyl) amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N- (oxolan-2-ylmethyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-
(N-cyclohexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (3,3-dimethyl-
2-azetidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3-isocyanatophenyl) titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-hexyl- (4
-Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (4-tolylsulfonyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-
Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- ( 2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-butyl- (2-
Chloromethyl-2-methyl-3-chloropropanoyl)
Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (Phenylthiocarbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3-isocyanatophenyl) titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-hexyl- (4
-Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (4-tolylsulfonyl) amino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-
Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (N-butyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-(3-phenylpropanoyl) -2,2-dimethyl-
3-chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-cyclohexylmethyl-
(2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N-isobutyl-
(2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N-butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (Butylthiocarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6 -Difluoro-3-
(N-hexyl-2,2-dimethylbutanoyl) amino) phenyl] titanium,

Bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-
Dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2
6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N- (2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N
-Butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2, -trimethylpropyl) dimethylsilylamino) phenyl] Titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-allyloxy) Methyl-3-methyl-
2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-
3- (3-chloromethyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2- Dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,
6-diphenyl-2-piperidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N- (2,3-dihydro-1,
2-benzisothiazolo-3-one (1,1-dioxide) -2-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) ) Amino) phenyl]
Titanium, bis (cyclopentadienyl) bis [2,6-
Difluoro-3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino] ) Phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (4-methylphenylmethyl)-(4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 4-methylphenylmethyl)-
(2-chlorobenzoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethyl) Pentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2
6-difluoro-3- (N- (2-ethylhexyl)-
4-tolyl-sulfonyl) amino) phenyl] titanium,
Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoromethylsulfonyl) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,
6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl)
Bis [2,6-difluoro-3- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,
6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-
Dimethyl-7-methoxyoctyl) benzoylamino)
Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium, and the like.

Examples of (j) active ester compounds which are other examples of the photopolymerization initiator include imide sulfonate compounds described in JP-B-62-6223 and JP-B-63-14340.
And active sulfonates described in JP-A-59-174831.

Preferred examples of the compound having a carbon-halogen bond (k), which is an example of a photopolymerization initiator, include those represented by the following general formulas [IV] to [X].

[0090]

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(Wherein X ² represents a halogen atom; Y ^{2
_{-C (X 2) 3, -NH}} 2, -NHR 3 2, -NR 32, the -
Represent OR ^32. Here, R ³² represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Also R ³¹
Represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

[0092]

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(Where R ³³ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group; ^Three
Is a halogen atom, and n is an integer of 1 to 3. ).

[0094]

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(Where R ³⁴ is an aryl group or a substituted aryl group, and R ³⁵ is

[0096]

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Or Z ² is —C (＝ O)
—, —C (＝ S) — or —SO ₂ —, and R ³⁶ , R ³⁷
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group;
³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. ).

[0098]

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In the formula, R ³⁹ is an optionally substituted aryl group or a heterocyclic group, and R ⁴⁰ is carbon atom 1
A trihaloalkyl or trihaloalkenyl group having up to 3; and p is 1, 2 or 3.

[0100]

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(Where L is a hydrogen atom or a compound of the formula: CO—
(R ⁴¹ ) q (C (X ⁴ ) ₃ ) r is a substituent, and Q represents a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or an N group.
-R group, M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, R ⁴² is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R ⁴¹ is X ⁴ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1, or q = 1 and r =
1 or 2. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group;

[0102]

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(Where X ⁵ is a halogen atom, t
Is an integer of 1 to 3, s is an integer of 1 to 4, R ⁴³
A hydrogen atom or a CH _3-t X _5t group, R ⁴⁴ is represented by a is) s-valent optionally substituted unsaturated organic group, 4- halogeno-5- (halogenomethyl-phenyl) -
-Oxazole derivatives.

[0104]

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(Where X ⁶ is a halogen atom;
Is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁵
Is a hydrogen atom or a CH _3-v X _6v group, R ⁴⁶ is an unsaturated organic group which may be substituted for u-valent. ), A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Specific examples of such a compound having a carbon-halogen bond include, for example, Wakabayashi et al., Bull.
em. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis ( Trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S -Triazine, 2- (2 ', 4'-dichlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2,
4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-
Trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other compounds described in GB 1388492, for example, 2
-Styryl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
(Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
Compounds described in JP-A-53-133428, such as -4-amino-6-trichloromethyl-S-triazine, for example, 2- (4-methoxy-naphth-1-yl) -4,6
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphth-5-
Yl) -4,6-bis-trichloromethyl-S-triazine and the like, the compounds described in DE 3337024, for example,

[0107]

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[0108]

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And the like. Also, FC Sc
Haefer et al., J. Org. Chem. 29, 1527 (196
The compounds described in 4), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,6-tris (dibromomethyl) -S-triazine,
2-amino-4-methyl-6-tribromomethyl-S-
Triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, compounds described in JP-A-62-58241, for example,

[0110]

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[0111]

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And the like. Further, Japanese Patent Laid-Open No. 5-
No. 281,728, for example,

[0113]

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And the like. Or even
Jou by MP Hutt, EF Elslager and LM Herbel
rnalof Heterocyclic chemistry ", Vol. 7 (No.
3) The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis methods described on pages 511 et seq. (1970).

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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Alternatively, compounds such as those described in German Patent No. 2641100, for example 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in DE 33 33 450, for example,

[0122]

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In the formula, R ⁴¹ represents a benzene ring, and R ⁴² represents an alkyl group, an aralkyl group or an alkoxyalkyl group.

[0124]

[Table 2]

Alternatively, a group of compounds described in German Patent No. 3021590,

[0126]

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[0127]

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Alternatively, a group of compounds described in German Patent No. 3021599, for example,

[0129]

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The following can be mentioned. Even more preferred examples of the photopolymerization initiator in the present invention include the above-mentioned (a) aromatic ketones, (b) aromatic onium salt,
Examples thereof include (c) an organic peroxide, (e) hexaarylbiimidazole, (i) a metallocene compound, and (k) a compound having a carbon-halogen bond. As the most preferable examples, aromatic iodonium salts and aromatic compounds Group diazonium salts, titanocene compounds, and trihalomethyl-S-triazine compounds represented by the general formula [IV]. The photopolymerization initiator in the present invention is suitably used alone or in combination of two or more. next,
The sensitizing dye that can be a component of the photopolymerizable composition of the present invention includes a spectral sensitizing dye, and a dye or pigment that absorbs light from a light source and interacts with a photopolymerization initiator.

Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene) and xanthenes (eg, fluorescein, eosin,
Erythrosine, rhodamine B, rose bengal cyanines (eg, thiacarbocyanine, oxacarbocyanine) merocyanines (eg, merocyanine, carbomerocyanine) thiazines (eg, thionin, methylene blue, toluidine blue) acridines (eg, acridine orange, Chloroflavin, acriflavin) phthalocyanines (eg, phthalocyanine, metal phthalocyanine) porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin) chlorophylls (eg, chlorophyll, chlorophyllin, central metal-substituted chlorophyll) metal complexes, eg,

[0132]

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Anthraquinones (for example, anthraquinone) and squariums (for example, squarium). Examples of more preferred spectral sensitizing dyes or dyes are styryl dyes described in JP-B-37-13034, for example,

[0134]

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Cationic dyes described in JP-A-62-143044, for example,

[0136]

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Quinoxalinium salts described in JP-B-59-24147, for example,

[0138]

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New methylene blue compounds described in JP-A-64-33104, for example,

[0140]

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Anthraquinones described in JP-A-64-56767, for example,

[0142]

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Benzoxanthene dyes described in JP-A-2-1714. JP-A-2-226148 and JP-A-2-2-2
No. 26149, acridines, for example,

[0144]

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Pyrylium salts described in JP-B-40-28499, for example,

[0146]

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Cyanines described in JP-B-46-43363, for example,

[0148]

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Benzofuran dyes described in JP-A-2-63053, for example,

[0150]

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JP-A-2-85858, JP-A-2-21
No. 6154 conjugated ketone dyes, for example

[0152]

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Dyes described in JP-A-57-10605. Azocinnamylidene derivatives described in JP-B-2-30321, for example,

[0154]

[Of 60]

Cyanine dyes described in JP-A-1-287105, for example,

[0156]

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JP-A-62-31844, JP-A-62-31844
No. 31848, Xanthene dyes described in JP-A-62-143043, for example,

[0158]

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An aminostyryl ketone described in JP-B-59-28325, for example,

[0160]

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Merocyanine dyes represented by the following formulas [1] to [8] described in JP-B-61-9621, for example,

[0162]

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In the general formulas [3] to [8], X ⁸
Is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, a substituted aryl group, an aryloxy group,
Represents an aralkyl group or a halogen atom. General formula [2]
In the above, Ph represents a phenyl group. In the general formulas [1] to [8], R ⁴⁸ , R ⁴⁹ and R ⁵⁰ each represent an alkyl group, a substituted alkyl group, an alkenyl group, an aryl group, a substituted aryl group or an aralkyl group. Good. The following general formula described in Japanese Patent Application Laid-Open No. H2-179643

Dyes represented by [9] to [11], for example,

[0164]

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A: oxygen atom, sulfur atom, selenium atom,
Represents a tellurium atom, an alkyl or aryl substituted nitrogen atom or a dialkyl substituted carbon atom. Y ^{3 represents a} hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group, or a substituted alkoxycarbonyl group. R ⁵¹ and R ⁵² : a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
Alternatively, as a substituent, R ⁵³ O—,

[0166]

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-(CH ₂ CH ₂ O) w-R ⁵³ , a substituted alkyl group having 1 to 18 carbon atoms and having a halogen atom (F, Cl, Br, I). However, R ⁵³ is a hydrogen atom or a carbon number of 1 to 1.
0 represents an alkyl group, B represents a dialkylamino group,
Represents a hydroxyl group, an acyloxy group, a halogen atom, and a nitro group. w represents an integer of 0 to 4; x represents an integer of 1 to 20; The following general formula [1] described in JP-A-2-244050
2) a merocyanine dye represented by, for example,

[0168]

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(Wherein R ⁵⁴ and R ⁵⁵ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group. A ² represents an oxygen atom, a sulfur atom , A selenium atom, a tellurium atom, an alkyl or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, and X ⁹ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring. ⁴ represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring, and Z ³ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Represents an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group, which may be mutually bonded to Y ⁴ to form a ring. Preferred specific examples are

[0170]

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A merocyanine dye represented by the following general formula [13] described in JP-B-59-28326, for example,

[0172]

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In the above formula, R ⁵⁶ and R ⁵⁷ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Represents a substituted aryl group or an aralkyl group, which may be the same or different from each other. X ¹⁰ is Hammett (Hamm
ett) represents a substituent within the range of -0.9 to +0.5. A merocyanine dye represented by the following general formula [14] described in JP-A-59-89303, for example,

[0174]

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(Wherein R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an aralkyl group. X ¹¹ is Hammett's sigma (σ)) Values from -0.9 to +0.
Represents up to 5 substituents. Y ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an acyl group or an alkoxycarbonyl group. As a preferred specific example,

[0176]

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A merocyanine dye represented by the following general formula [15] described in JP-A-8-129257, for example,

[0178]

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(Wherein R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁸ ,
R ⁶⁹ , R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group, a substituted phosphonato group, a cyano group, or a nitro group, or, R ⁶⁰ and R ^61, R ⁶¹ and R ^62, R ⁶² and R ^63, R ⁶⁸ and R ^69, R ⁶⁹ and R ^70, R ⁷⁰ And R
⁷¹ may combine with each other to form an aliphatic or aromatic ring, R ⁶⁴ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group; R ⁶⁵ represents a substituted or unsubstituted group; substituted alkenyl group, or a substituted or unsubstituted alkynyl group, R ^66, R ⁶⁷
Are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Preferred examples of the substituted carbonyl group)

[0180]

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A benzopyran-based dye represented by the following general formula [16] described in JP-A-8-334897, for example,

[0182]

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(Wherein, R ^{72 to} R ⁷⁵ independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group; and R ^{72 to} R ⁷⁵
May form a ring composed of non-metallic atoms together with the carbon atoms to which they can each be attached. R ⁷⁶ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁷⁷
Is a group represented by R ⁷⁶ or —Z—R ⁷⁶ , and Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁷⁶ and R ⁷⁷ may together form a ring composed of a non-metallic atom. A is O atom, S
Represents an atom, NH or an N atom having a substituent. B is O
Represents an atom or a group of = C (G1) (G2). G1, G2
May be the same or different, and represent a hydrogen atom, a cyano group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluorosulfonyl group. However, G1 and G2 are not simultaneously hydrogen atoms. G1 and G2 may form a ring composed of a nonmetallic atom together with the carbon atom). And the like.

In addition, the following infrared absorbers (dyes or pigments) are particularly preferably used as sensitizing dyes. Preferred examples of the dye include, for example, JP-A-58-12524.
No. 6, JP-A-59-84356, JP-A-59-202
No. 829, JP-A-60-78787 and the like, and cyanine dyes described in British Patent No. 434,875.

The near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and further, the substituted sensitizer described in US Pat. No. 3,881,924 is used. Arylbenzo (thio) pyrylium salts described in JP-A-57-142645 (U.S. Pat. No. 4,327,169).
No. 5) Trimethine thiapyrylium salts described in JP-A-58-181051, JP-A-58-220143, and JP-A-58-220143.
Nos. 9-41363, 59-84248 and 59-8
No. 4249, No. 59-146063, No. 59-146
No. 061, JP-A-5961
Cyanine dyes described in JP-A-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication Nos.
Pyrylium compounds described in 19702 are also preferably used.

Also preferred are near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513 A2. It can be mentioned as.

Further, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. The anionic infrared absorbing agent refers to a dye that substantially has no anionic structure in the mother nucleus of a dye that absorbs infrared light and has an anionic structure. For example, (c1) an anionic metal complex, (c2) anionic carbon black,
(C3) Anionic phthalocyanine, and (c4) a compound represented by the following general formula 6 and the like. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

[0188]

[Of 75]

Here, the (c1) anionic metal complex refers to an anion in which the central metal and the ligand in the complex part that substantially absorbs light become anions.

(C2) The anionic carbon black is
Examples of the substituent include carbon black to which an anionic group such as a sulfonic acid, a carboxylic acid, and a phosphonic acid group is bonded. To introduce these groups into carbon black,
Carbon Black Handbook Third Edition (edited by The Carbon Black Association, April 5, 1995)
As described on page 12, means such as oxidation of carbon black with a predetermined acid may be employed.

(C3) Anionic phthalocyanine refers to an anionic phthalocyanine in which the anion group described in (c2) above is bonded as a substituent to the phthalocyanine skeleton to form an anion as a whole.

Next, the compound (c4) represented by the general formula 6 will be described in detail. Wherein in formula 6, G _a ^-
Represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a cation having 1 to m valence including a proton, and m represents an integer of 1 to 6. M represents a conjugated chain,
This conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

[0193]

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In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
It represents an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group, and these may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

Among the anionic infrared absorbers represented by the above formula 6, those having the following A-1 to A-5 are preferably used.

[0196]

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Also, cationic infrared absorbers represented by the following CA-1 to CA-44 can be preferably used.

[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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In the above structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ ,
Br ⁻ , I ⁻ ), Lewis acid anions (BF ₄ −, PF ₆ ⁻ ,
SbCl ₆ ⁻ , ClO ₄ ⁻ ), an alkylsulfonic acid anion and an arylsulfonic acid anion.

[0214] The alkyl of the alkylsulfonic acid is
A linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl,
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 a cyclic alkyl group having 5 to 10 carbon atoms is more preferred.

The aryl of the above-mentioned arylsulfonic acid includes one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and a benzene ring and a 5-membered unsaturated ring forming a condensed ring. And as a specific example,
Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

Further, nonionic infrared absorbers represented by the following NA-1 to NA-12 can also be preferably used.

[0219]

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[0218]

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[0219]

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[0220]

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Among the above exemplified compounds, A-1 is particularly preferred as the anionic infrared absorber, CA-7, CA-30, CA-40 and CA-42 are preferred as the cationic infrared absorber, and nonionic surfactants are preferred. NA as infrared absorber
-11.

As other dyes, commercially available dyes and, for example, “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970)
And the like can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, diimmonium dyes, aminium dyes, squalilium dyes, metal thiolate complexes and the like Is mentioned.

As other sensitizing dyes, commercially available pigments and Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977)
Annual Publication), “Latest Pigment Application Technology” (CMC Publishing, 1986)
Pigments described in "Printing Ink Technology", CMC Publishing, 1984). For example, the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The surface treatment method is described in "Properties and Applications of Metal Soap" (Koshobo)
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably from 0.01 μm to 10 μm, more preferably from 0.05 μm to 1 μm, particularly preferably from 0.1 μm to 1 μm. When the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the coating solution for the image recording layer, and when it exceeds 10 μm, the uniformity of the image recording layer is not preferred.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

More preferred examples of the sensitizing dye in the present invention include the merocyanine dye described in JP-B-61-9621, the merocyanine dye described in JP-A-2-179463, and the merocyanine described in JP-A-2-244050. Dyes, merocyanine dyes described in JP-B-59-28326, merocyanine dyes described in JP-A-59-89303, merocyanine dyes described in JP-A-8-129257, and benzopyran-based dyes described in JP-A-8-334897 are listed. Can be. And the above-mentioned JP-A-11-2
The infrared absorber described in No. 09001 can be mentioned. The sensitizing dye in the present invention is also preferably used alone or in combination of two or more. Further, a known compound having an action of further improving sensitivity or suppressing polymerization inhibition by oxygen may be added to the photopolymerizable composition of the present invention as a cosensitizer.

Examples of such co-sensitizers include amines, for example, MR Sander et al., Journal of Polymer Soc.
Society, Vol. 10, p. 3173 (1972);
No. 20189, JP-A-51-82102, JP-A-52
-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 3382
No. 5, and the like, and specific examples thereof include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806 and JP-A-5-142772, No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is mentioned.

Another example includes amino acid compounds (eg, N-phenylglycine, etc.) and JP-B-48-429.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, sulfur compounds described in JP-A-6-308727 (eg, trithiane, etc.), JP-A-6-250389. No. 6 (Diethyl phosphite, etc.)
191605, Si-H and Ge-H compounds.

The amount of the photopolymerization initiator to be used in the composition of the present invention is from 0.01 to 0.01 based on the weight of all components of the photopolymerizable composition.
It is 60% by weight, more preferably 0.05 to 30% by weight. When a sensitizing dye is used in the present invention, the molar ratio of the photopolymerization initiator and the sensitizing dye in the photopolymerizable composition is 100: 0 to 0.
1:99, more preferably 90:10 to 10:
90, most preferably from 80:20 to 20:80. When using the above co-sensitizer, the photopolymerization initiator 1
It is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, and most preferably 0.05 to 10 parts by weight with respect to parts by weight.

The photosensitive layer composition of the lithographic printing plate precursor according to the invention preferably contains a linear organic high molecular polymer as a binder. As such a “linear organic high molecular polymer”, any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Absent. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film-forming agent of the composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include addition polymers having a carboxylic acid group in a side chain, for example, JP-A-59-44615 and JP-B-54-3.
4327, JP-B-58-12577, JP-B-54-
25957, JP-A-54-92723, JP-A-59
No.-53836 and JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, There are partially esterified maleic acid copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, an alcohol-soluble polyamide, a polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

Any of these linear organic high molecular weight polymers can be incorporated in the whole composition. However, if the amount exceeds 90% by weight based on the weight of all components of the composition, no favorable result is obtained in terms of the strength of the formed image and the like. Preferably it is 30 to 85%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer is 1 to 1.
It is preferably in the range of / 9 to 7/3. A more preferred range is 3/7 to 5/5. However, when a high molecular compound is used as the compound having the structure represented by the general formula (I) of the present invention, since the compound itself has a function as a binder, the compound described above is contained in the photopolymerizable composition. It does not have to contain a binder. When used by mixing with a binder, the ratio of the polymerizable compound of the present invention to the binder can be used in the above-mentioned weight ratio.

Polymerization Inhibitor In the present invention, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photopolymerizable composition in addition to the above basic components is prevented. For this purpose, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. Good. The amount of the higher fatty acid derivative to be added is about 0.5% by weight of the total composition.
About 10% by weight is preferred.

Colorant, etc. Further, a dye or pigment may be added for the purpose of coloring the photosensitive layer. This makes it possible to improve the so-called plate inspection, such as the visibility of the printing plate after plate making and the suitability for an image density measuring device. As many colorants, pigments are particularly preferable because many dyes lower the sensitivity of the photopolymerizable photosensitive layer. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of the dye or pigment added is preferably about 0.5% to about 5% by weight of the total composition.

Other additives In order to improve the physical properties of the cured film, known additives such as inorganic fillers, other plasticizers, and oil-sensitizing agents capable of improving the ink adhesion on the surface of the photosensitive layer are also used. May be added. Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like.When a binder is used,
It can be added in an amount of 10% by weight or less based on the total weight of the compound having an ethylenically unsaturated double bond and the binder.
Further, a UV initiator, a thermal crosslinking agent, and the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later.

In addition, additives for improving the adhesion between the photosensitive layer and the support and for improving the development removability of the unexposed photosensitive layer,
It is possible to provide an intermediate layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, the adhesion can be improved and the printing durability can be increased. Addition of an acid or a hydrophilic polymer such as polysulfonic acid or undercoating improves the developability of the non-image area and improves the stainability.

When coating the photopolymerizable composition of the present invention on a support, it is used after dissolving it in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight.

The amount of the photosensitive layer coated on the support mainly affects the sensitivity of the photosensitive layer, the developability, and the strength and printing durability of the exposed film, and is desirably appropriately selected depending on the application. If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, the exposure takes time, and the developing process requires a longer time, which is not preferable. As is the principal object lithographic printing plate for scan exposure of the present invention, the coating amount in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying is suitable. More preferably 0.5 to
It is 5 g / m ² .

[Support] In order to obtain the lithographic printing plate precursor according to the invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) Such metals include paper or plastic films on which the metal is laminated or vapor-deposited, and these surfaces are subjected to known physical and chemical treatments suitable for the purpose of imparting hydrophilicity and improving the strength as necessary. May be applied.

Particularly preferred examples of the support include paper, a polyester film and an aluminum plate. Among them, it has good dimensional stability, is relatively inexpensive, and has excellent hydrophilicity and strength by surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.4 mm.
mm to 0.3 mm.

In the case of a support having a metal surface, particularly an aluminum surface, a roughening (graining) treatment, an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing Preferably, a surface treatment such as a treatment is performed.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method and a polishing method can be used. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, a method combining both of them can be used as disclosed in JP-A-54-63902. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove the rolling oil on the surface.

Further, an aluminum plate which has been roughened and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is performed, for example, in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. This is performed by flowing a current using an aluminum plate as an anode.

Also, silicate electrodeposition as described in US Pat. No. 3,658,662 is effective. Furthermore, JP-B-46-27481 and JP-A-52-5860.
No. 2, Japanese Patent Application Laid-Open No. 52-30503, and a surface treatment obtained by combining the support subjected to electrolytic graining with the above anodic oxidation treatment and sodium silicate treatment are also useful.
It is also preferable to sequentially perform mechanical roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893. Furthermore, after performing these treatments, water-soluble resins, such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid,
A water-soluble metal salt (eg, zinc borate) or a yellow dye,
A primer coated with an amine salt or the like is also suitable.

Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is also preferably used. Other preferred examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. As such a surface layer, for example, US30
No. 55295, a layer comprising an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, a titanium oxide and a polyvinyl oxide described in JP-A-8-507727. A sol-gel film made of alcohol or silicic acid can be used. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to improve the adhesion of the photosensitive layer. Etc.

"Protective layer" In the present invention, in the lithographic printing plate for scanning exposure, since the exposure is usually performed in the air, a protective layer can be further provided on the photosensitive layer of the photopolymerizable composition. . The protective layer prevents a low molecular compound such as a basic substance present in the atmosphere that inhibits an image forming reaction caused by exposure in the photosensitive layer from being mixed into the photosensitive layer, and enables exposure in the atmosphere. Therefore, the property desired for such a protective layer is that the low molecular compound has low permeability, and further, does not substantially inhibit the transmission of light used for exposure, has excellent adhesion to the photosensitive layer, and Desirably, it can be easily removed in a developing step after exposure. Such a contrivance for the protective layer has been conventionally made, and US Pat. No. 3,458,3.
No. 11 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used, and specifically, polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum arabic, and polystyrene. Although water-soluble polymers such as acrylic acid are known, use of polyvinyl alcohol as the main component gives the best results in terms of basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component. As a specific example of polyvinyl alcohol, 71 to 100 mol% is hydrolyzed,
Those having a weight average molecular weight in the range of 300 to 2400 can be mentioned. Specifically, Kuraray's PVA-105, PVA-110, and PVA-11
7, PVA-117H, PVA-120, PVA-12
4, PVA-124H, PVA-CS, PVA-CS
T, PVA-HC, PVA-203, PVA-204,
PVA-205, PVA-210, PVA-217, P
VA-220, PVA-224, PVA-217EE,
PVA-217E, PVA-220E, PVA-224
E, PVA-405, PVA-420, PVA-61
3, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), coating amount, etc. are selected in consideration of fogging properties, adhesion and scratch resistance in addition to low molecular substance blocking properties and development removability. .
Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the barrier properties of low molecular substances, which is advantageous in terms of sensitivity. . However, if the low-molecular substance blocking property is extremely increased, an unnecessary polymerization reaction occurs during production or raw storage,
Further, at the time of image exposure, there is a problem that unnecessary fogging and thickening of image lines occur. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesive strength tends to occur. On the other hand, various proposals have been made to improve the adhesiveness between these two layers. For example, U.S. Pat. No. 2,925,501 and U.S. Pat. No. 44,563 disclose mixing an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol in an amount of 20 to 60% by weight. It is described that sufficient adhesiveness can be obtained by laminating on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer, for example, US Pat.
458, 311 and JP-A-55-49729.

Further, other functions can be imparted to the protective layer. For example, when a laser beam is used as a light source, the photosensitive composition may have excellent photosensitivity at the wavelength of the light source, but may not want to be exposed at other wavelengths. For example, if the light source is in the infrared region of 750 nm or more, the light source can be used substantially in a bright room, but in practice, it may be exposed to short-wave light such as light from a fluorescent lamp. In this case, it is preferable to add a colorant (a water-soluble dye or the like) which is excellent in light transmittance of the light source and can efficiently absorb light having a wavelength of less than 700 nm. As another example, the light source is 45
If it is in the ultraviolet region of 0 nm or less, it can be used substantially under safelight. But in fact, 50
It may be exposed to visible light of 0 nm or more. In this case, the addition of a colorant (such as a water-soluble dye), which is excellent in light transmittance of the light source and can efficiently absorb light of 500 nm or more, further enhances safe light suitability without lowering sensitivity. be able to.

When a photosensitive material using the photopolymerizable composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. . Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate are JP-B-57-74.
No. 27, such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate and tertiary phosphorus. Ammonium acid,
Aqueous solutions of inorganic alkali agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Also, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

In the plate making process of the lithographic printing plate precursor according to the invention, if necessary, the entire surface may be heated before exposure, during exposure, or between exposure and development. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement of sensitivity and printing durability and stabilization of sensitivity can be brought about. Furthermore, for the purpose of improving image strength and printing durability,
It is also effective to heat the entire surface of the image after development or to expose the entire surface. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, there arises a problem that a non-image portion is covered.
Very strong conditions are used for heating after development. Usually 2
The range is from 00 to 500 ° C. If the temperature is low, sufficient image strengthening action cannot be obtained, and if the temperature is too high, deterioration of the support,
Problems such as thermal decomposition of the image area occur. Known methods can be used for the exposure method of the scanning exposure planographic printing plate according to the present invention without any limitation. A laser is preferred as the light source.
For example, as an available laser light source having a wavelength of 350 to 450 nm, the following can be used.

As a gas laser, an Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), a Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He-
Cd laser (441nm, 325nm, 1mW ~ 100m
W), a combination of Nd: YAG (YVO ₄ ) and SHG crystal × 2 times (355 mm, 5 mW to 1
W), Cr: Combination of LiSAF and SHG crystal (4
30nm, 10mW), KNbO as a semiconductor laser system
_3. Ring resonator (430 nm, 30 mW), combination of waveguide type wavelength conversion element and AlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350nm, 5mW ~ 100mW),
AlGaInN (350 nm to 450 nm, 5 mW to 30 mW) Other pulsed laser as a N ₂ laser (337N
m, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ)

Particularly, among these, an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410n)
m, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost. In addition, available light sources of 450 nm to 700 nm include Ar + laser (488 nm), YAG-SHG laser (532 nm), and He-Ne laser (633 n).
m), He-Cd laser, red semiconductor laser (65
Semiconductor lasers (800 to 850 nm) as available light sources of 700 nm to 1200 nm.
m), Nd-YAG laser (1064 nm) can be suitably used. In addition, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp,
Metal halide lamps, ultraviolet laser lamps (ArF excimer lasers, KrF excimer lasers, etc.), and radiation such as electron beams, X-rays, ion beams, and far-infrared rays can also be used. Particularly preferred.

The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type and the like. The photosensitive layer component of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one.However, a lithographic printing plate having such a configuration can be used on a printing press. After loading, a system such as exposure-development can be performed on the machine.

[0257]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. [Example 1] An aluminum plate of material 1S having a thickness of 0.30 mm was grained with a No. 8 nylon brush and an aqueous suspension of 800 mesh pumistone, and the surface was grained, followed by thorough washing with water. 60% at 70 ° C in 10% sodium hydroxide
After dipping for 2 seconds and etching, washing with running water, 20%
The resultant was neutralized and washed with HNO ₃ and washed with water. V _A = 12.7V
The electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution at an anode electricity of 300 coulomb / dm ² using a sinusoidal alternating current under the conditions described in (1). The surface roughness was measured.
It was 45 μm (Ra indication). After immersion in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on a grained surface in a 20% H ₂ SO ₄ aqueous solution at 33 ° C. When anodized at 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² . On the thus treated aluminum plate, a high-sensitivity photopolymerizable composition 1 having the following composition having a dry coating weight of 1.
The composition was applied so as to be 5 g / m ² and dried at 100 ° C. for 1 minute to form a photosensitive layer.

(Photopolymerizable Composition 1) Ethylenic unsaturated bond-containing compound (A1) 1.5 parts by weight Linear organic high molecular polymer (B1) 2.0 parts by weight Sensitizer (C1) 0.15 Parts by weight Photopolymerization initiator (D1) 0.2 parts by weight ε-phthalocyanine (F1) dispersion 0.02 parts by weight Fluorine nonionic surfactant Megafac F177 0.03 parts by weight (Dainippon Ink & Chemicals, Inc.) Methyl ethyl ketone 9.0 parts by weight Propylene glycol monomethyl ether acetate 7.5 parts by weight Toluene 11.0 parts by weight

[0259]

Embedded image

On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 500) was applied so that the dry coating weight was 2.5 g / m ² ,
It was dried at 120 ° C. for 3 minutes to obtain a lithographic printing plate precursor.

The lithographic printing plate precursor was treated with an FD / YAG laser (CSI plate jet 4) at 100 μJ /
After scanning and exposing a solid image and a 1-99% halftone dot image (in 1% increments) at 4,000 lines / inch and 4000 dpi at an exposure dose of cm ² , developer 1 and finishing gum solution FP Standard processing was performed using an automatic developing machine (LP-850P2 manufactured by Fuji Photo Film) charged with -2W (manufactured by Fuji Photo Film). The preheating condition is that the plate surface temperature is 1
00 ° C, developer temperature is 30 ° C, and immersion time in the developer is about 1
5 seconds. The developer 1 has the following composition and the pH is 2
It was 11.5 at 5 ° C. and the conductivity was 5 mS / cm.

(Composition of Developer 1) Potassium hydroxide 0.15 g Polyoxyethylene phenyl ether (n = 13) 5.0 g Cherest 400 (chelating agent) 0.1 g Water 93.75 g

[Examples 2 to 7] The compound (A1) containing an ethylenically unsaturated bond and the linear organic high molecular polymer (B1) of Example 1 were changed as shown in Table 1 below. In the same manner as in Example 1, a lithographic printing plate precursor was prepared and its performance was evaluated.

[0264]

[Table 3]

[0265]

[Table 4]

The lithographic printing plates obtained by the plate making methods of Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated for printing durability and printing smear. Printing durability is R2 manufactured by Man Roland.
Using a 01 type printing machine, printing was performed using GEOS G black (N) manufactured by Dainippon Ink Co., Ltd., and the evaluation was made based on the number of prints at which the solid portion was worn and the ink was not deposited. The print stain is a diamond IF2 type printer manufactured by Mitsubishi Heavy Industries, and GEO manufactured by Dainippon Ink.
Printing was performed using SG Red (S), and ink stains in the non-image areas were visually evaluated. Table 2 shows the results.

[0267]

[Table 5]

As is clear from Table 2, the lithographic printing plate precursors of the examples according to the present invention showed higher printing durability than the lithographic printing plate precursors of Comparative Examples.

[0269]

According to the lithographic printing plate precursor of the present invention, the photosensitive layer contains a monomer compound having two or more specific imide acrylate structures in one molecule, thereby achieving high sensitivity and photopolymerization. The part became a tough cured film, high printing durability and excellent stain resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA12 AB03 AC01 AC08 AD01 BC13 BC34 BC42 BC83 FA10 FA17 2H096 AA06 BA05 EA02 EA04 EA23 GA08 2H114 AA04 AA22 AA23 BA02 BA10 DA52 EA01 EA02 EA03 GA03 GA04 GA08 GA09 AL67P BC65P BC66P CA01 CA04 JA37

Claims (1)

[Claims] 1. A lithographic printing plate precursor having a photopolymerizable photosensitive layer containing a compound having two or more structures represented by the following general formula (I) in one molecule. Embedded image (R ₁ represents H or an alkyl group having 1 to 5 carbon atoms, R ₂
Represents an alicyclic or aromatic ring residue having 6 carbon atoms. )