JP2002287344A - Photopolymerizable planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable planographic printing plate having high sensitivity and also having good storage stability while retaining handleability in a light room. SOLUTION: The photopolymerizable planographic printing plate has a photosensitive layer containing a photopolymerization initiator, an aliphatic polymerizable compound and an aromatic polymerizable compound as two polymerizable compounds on an aluminum base. The photopolymerization initiator preferably contains >=4 aromatic rings in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable lithographic printing plate, and more particularly, to a photopolymerizable lithographic printing plate having high sensitivity, good storage stability and good light room handling.

[0002]

2. Description of the Related Art In the field of photosensitive lithographic printing plate precursors, 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 manufactured with high output and small size. These lasers are now available, and are very useful as recording light sources when making plates directly from digital data from a computer or the like. Various studies have been made on lithographic printing plate precursors (hereinafter, also simply referred to as recording materials) that are sensitive to these various laser beams. As a typical example, first, recording is possible with an infrared laser having a photosensitive wavelength of 760 nm or more. As the material, a positive recording material described in U.S. Pat. No. 4,708,925,
Secondly, an acid-catalyzed cross-linkable negative recording material described in JP-A-8-276558 is used in the range of 300 nm to 7 nm.
No. 2,850,445 and Japanese Patent Publication No. 44-2 are examples of recording materials compatible with ultraviolet or visible light lasers of 00 nm.
There are many radical polymerization type negative recording materials described in Japanese Patent No. 0189.

Among them, radical photopolymerization type is highly sensitive and is advantageous for a so-called direct printing plate in which the image is exposed directly to the plate by a computer from various lasers without using a conventional lith film. In the field of the direct printing plate, 488 nm, 532
The combination of a visible light laser light source such as nm and a photopolymerizable lithographic printing plate has been put to practical use, but in addition to the need for higher sensitivity in order to respond to the increase in drawing speed in pursuit of higher productivity, In terms of workability, the demand for handling (light room) under a yellow light or white light instead of a dark room is increasing.

Further, in order to improve the sensitivity, a photopolymerization initiator or a photopolymerization initiation system has been designed and developed, and various compounds have been used. However, such a photopolymerization initiator has poor compatibility in the photosensitive layer, and sometimes lowers sensitivity and storage stability (especially when increasing the amount for higher sensitivity). For example, a photopolymerization initiator that attracts attention as a highly sensitive photopolymerization initiator is a photopolymerization initiator containing four or more aromatic rings in the molecule. Such a photopolymerization initiator containing four or more aromatic rings in the molecule contains a large amount of aromatic rings, so that the sensitizing effects such as energy transfer and electron transfer are improved, and the photopolymerization initiator is thermally stable. Compound. Also,
Many do not absorb visible light, and a photosensitive composition containing the same can be made brighter by combining it with an exposure method such as an ultraviolet-violet laser having a wavelength of 300 nm to 450 nm and an infrared laser having a wavelength of 800 to 1200 nm. It is becoming.

[0005]

However, unfortunately,
A photopolymerization initiator containing four or more aromatic rings in the molecule becomes a highly planar molecule because it contains many aromatic rings,
Since the crystallinity and the oil sensitivity are extremely high, the initiator may precipitate as crystals in the photosensitive layer when stored for a long period of time, and the sensitivity may decrease. Accordingly, an object of the present invention is to provide a photopolymerizable lithographic printing plate which overcomes the above problems and has high sensitivity and good storage stability while maintaining light room handling.

[0006]

Means for Solving the Problems As a result of diligent studies by the present inventors, what kind of photopolymerization initiator is obtained by using two kinds of polymerizable compounds, an aliphatic polymerizable compound and an aromatic polymerizable compound, in combination. When the compound is used, the compatibility in the photosensitive layer is good, and in particular, the photopolymerization initiator containing four or more aromatic rings in the molecule shows good compatibility, so that high sensitivity and lightness can be obtained. It has been found that the storage stability is improved while maintaining the room. That is, the present invention has the following configuration. (1) A photopolymerizable lithographic printing method having a photosensitive layer containing, on an aluminum support, a photopolymerization initiator and two kinds of an aliphatic polymerizable compound and an aromatic polymerizable compound as a polymerizable compound. Edition. (2) The photopolymerizable composition according to (1), wherein the photopolymerization initiator is an initiator containing four or more aromatic rings in a molecule.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Polymerizable compound] The polymerizable compound contained in the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention will be described. The polymerizable compound contained in the photosensitive layer of the photopolymerizable lithographic printing plate of the invention is an aliphatic polymerizable compound or an aromatic compound. In the present invention, the definition of the aliphatic polymerizable compound is a compound having an ethylenically unsaturated bond capable of addition polymerization that does not contain an aromatic group in the molecule, and the definition of the aromatic polymerizable compound is an addition polymerizable compound. The compound having at least one aromatic group in the molecule among compounds having a polymerizable ethylenically unsaturated bond.
General examples of the aliphatic polymerizable compound include, for example, esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, An amide of the above unsaturated carboxylic acid and an aliphatic polyamine compound is exemplified.

Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 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. Examples include dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, and sorbitol tetramethacrylate. 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.

Crotonic acid esters 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. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. 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. Methylene bis-methacrylamide, diethylenetriamine trisacrylamide and the like.

Another example is disclosed in 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 described in JP-A-51-37193, JP-A-48-64183.
No., JP-B-49-43191, JP-B-52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in Japanese Patent Publication No. 0 are mentioned. Furthermore, the Journal of the Adhesion Society of Japan vol.20, No. 7, pages 300 to 308 (19
(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.

General examples of the aromatic polymerizable compound include a reaction product of an aromatic polyhydroxy compound and glycidyl acrylate or glycidyl methacrylate.
Bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis [p- (acryloxyethoxy) phenyl] dimethylmethane and the like. Further, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid is exemplified, and examples thereof include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. As other aromatic monomers, allyl esters such as diallyl phthalate and acrylamides such as xylylenebisacrylamide can also be used. Further, as the aromatic group of the aromatic polymerizable compound, a heterocyclic aromatic group can also be suitably used. Specific examples of the aromatic polymerizable compound are shown below.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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In addition, an α-hetero type monomer having a structure represented by the general formula (I) described in Japanese Patent Application No. 11-268842 can be suitably used. Hereinafter, specific examples of the α-hetero type monomer will be shown.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

[0023]

[Table 5]

[0024]

[Table 6]

[0025]

[Table 7]

[0026]

[Table 8]

[0027]

[Table 9]

[0028]

[Table 10]

[0029]

[Table 11]

[0030]

[Table 12]

[0031]

[Table 13]

[0032]

[Table 14]

[0033]

[Table 15]

[0034]

[Table 16]

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The amount of all the polymerizable group-containing compounds used is usually 1 to 99.99%, preferably 5 to 90.0%, more preferably 10 to 70%, based on the weight of all components of the photosensitive layer.
Amount is used. (The percentages here are weight percentages).

Next, the photopolymerization initiator contained in the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention will be described. Although the photopolymerization initiator used in the present invention is not particularly limited, a photopolymerization initiator containing four or more aromatic rings in a molecule (hereinafter, also simply referred to as a photopolymerization initiator, a polymerization initiator or an initiator) is preferred. preferable. Preferred photopolymerization initiators containing four or more aromatic rings in the molecule include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, and (d) Hexaarylbiimidazole compounds,
(E) a borate compound, (f) a metallocene compound,
(G) a compound having a carbon-halogen bond.

Preferred examples of (a) aromatic ketones include “RADIATION CURING IN POLYMERSCIENCE AND TECHN”.
OLOGY '' JPFOUASSIER JFRABEK (1993), Compounds having a benzophenone skeleton or thioxanthone skeleton described in p77-117, for example,

[0046]

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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.
No. 47-23, JP-B-47-23
No. 664, benzoin derivatives described in JP-A-57-307.
Aroylphosphonic acid esters described in No. 04, JP-B-60
No. 26483 dialkoxybenzophenone, for example,

[0048]

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Further, as another example (b) of the aromatic onium salt, an element of Group V, VI and VII of the Periodic Table,
Specifically, N, P, As, Sb, Bi, O, S, Se,
Te, or an aromatic onium salt of I is included. Examples of such aromatic onium salts include JP-B-52-14.
No. 277, JP-B-52-14278, JP-B-52-1
No. 4279, and the like. In particular,

[0050]

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[0051]

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The following can be mentioned.

(C) Another example of the photopolymerization initiator used in the present invention, “organic peroxide” includes oxygen-
Almost all organic compounds having one or more oxygen bonds are included, such as 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone,
3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone.

Other examples of the photopolymerization initiator (d) hexaarylbiimidazole used in the present invention include:
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.

Examples of (e) borate salts, which are other examples of the photopolymerization initiator in the present invention, include compounds represented by the following general formula [I].

[0056]

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(Where R^{twenty two}, R^{twenty three}, R^{twenty four}And R^{twenty five}Is
May be the same or different from each other,
Unsubstituted alkyl group, substituted or unsubstituted aryl
Group, substituted or unsubstituted alkenyl group, substituted or
Unsubstituted alkynyl group or substituted or unsubstituted hetero
A ring group;^{twenty two}, R^{twenty three}, R^{twenty four}And R^{twenty five}Is two or more
The above groups may combine to form a cyclic structure. However,
R^{twenty two}, R^{twenty three}, R^{twenty four}And R ^{twenty five}At least one of the
A substituted or unsubstituted alkyl group. Z⁺Is alkaline
Shows metal cation or quaternary ammonium cation
). R above^{twenty two}~ R^{twenty five}Examples of the alkyl group include straight-chain,
Branched and cyclic ones, those having 1 to 18 carbon atoms
preferable. Specifically, methyl, ethyl, propyl, iso
Propyl, butyl, pentyl, hexyl, octyl,
Tearyl, cyclobutyl, cyclopentyl, cyclohexyl
And sill. As the substituted alkyl group,
A halogen atom (for example, -C
l, -Br, etc.), cyano group, nitro group, 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,
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 [I] 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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As another example of the metallocene compound (f) which is another example of the photopolymerization initiator, see 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-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-Ti-bis- 2,4,6-trifluorophenyl-1-
Yl, di-cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-
Ti-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 and bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium.

Preferred examples of the compound (g) having a carbon-halogen bond, which is one example of a photopolymerization initiator, include those represented by the following general formulas [II] to [VIII].

[0088]

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

[0090]

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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. ).

[0092]

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

[0094]

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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. ).

[0096]

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

[0098]

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(Where L is a hydrogen atom or a formula: CO—
(R ⁴¹ ) _q (C (X ⁴ ) ₃ ) a substituent of _r , wherein Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, an alkene-1,2-ylene group, a 1,2-phenylene group or N
-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. And a carbonylmethylene heterocyclic compound having a trihalogenomethyl group.

[0100]

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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
Is a hydrogen atom or a CH _3-t X ⁵ _t group, and R ⁴⁴ is an s-valent, optionally substituted unsaturated organic group).
4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives.

[0102]

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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 X6 _v 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, German Patent No. 333702.
No. 4 compounds, for example,

[0105]

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[0106]

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And the like. Furthermore, Japanese Unexamined Patent Publication No.
Compounds described in 2-58241, for example,

[0108]

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And the like.

Alternatively, MP Hutt, EF Elslag
er and LM Herbel, Journal of Heterocyclic che
The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Mistry”, Vol. 7 (No. 3), pp. 511 et seq. (1970).

[0111]

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[0112]

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

[0114]

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[0115]

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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 (b) aromatic onium salt, (c) organic peroxide, and (d)
Hexaarylbiimidazole, (f) a metallocene compound, (g) a compound having a carbon-halogen bond can be mentioned, and the most preferred examples include (d) hexaarylbiimidazole, a titanocene compound in (f). be able to. The photopolymerization initiator in the present invention is suitably used alone or in combination of two or more.

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. The photopolymerization initiator in the present invention can be referred to as a photopolymerization initiation system alone or as a mixture of sensitizing dyes described below.

The photopolymerizable composition used in the present invention contains the following in addition to the above-mentioned polymerization initiator. [Sensitizing Dye] Examples of the sensitizing dye that can be a component of the photopolymerizable composition of the present invention include 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,

[0119]

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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,

[0121]

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

[0123]

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The quinoxalinium salts described in JP-B-59-24147, for example,

[0125]

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

[0127]

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

[0129]

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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,

[0131]

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

[0133]

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

[0135]

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A benzofuran dye described in JP-A-2-63053, for example,

[0137]

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

[0139]

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

[0141]

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

[0143]

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

[0145]

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

[0147]

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

[0149]

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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,

[0151]

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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—,

[0153]

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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,

[0155]

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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

[0157]

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

[0159]

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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,

[0161]

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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 represents 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,

[0163]

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

[0165]

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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)

[0167]

[Of 60]

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

[0169]

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[0170] (wherein, R ⁷² to R ⁷⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. The R ⁷² to R ⁷⁵
May form a ring consisting of a nonmetallic atom 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 —ZR 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 916 513 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) an anionic phthalocyanine, and (c4) a compound represented by the following general formula (IX). The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

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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 (IX) will be described in detail. In the general formula 6,
G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a cation having 1 to m valences 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.

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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.

Of the anionic infrared absorbers represented by the general formula (IX), the following A-1 to A-5 are preferably used.

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

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[0187]

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[0195]

[Of 75]

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[0198]

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In the above structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ ,
Br ^-, I ^-), a Lewis acid anion _{^{(BF 4 -, PF 6 -}} , S
bCl ₆ ⁻ , ClO ₄ ⁻ ), an alkylsulfonic acid anion,
Aryl sulfonate anion.

The alkyl of the alkyl sulfonic 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. The specific example is,
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 absorbing agents represented by the following NA-1 to NA-12 can also be preferably used.

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

Other dyes include 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 being subjected to a surface treatment, or may be used after being subjected to a 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 photosensitive layer, and when it exceeds 10 μm, the uniformity of the photosensitive 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, and JP-A-56-142772. No. 75643, specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, and the like. Is raised.

Further, other examples include 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.

When a sensitizing dye is used in the present invention, the molar ratio of the photopolymerization initiator to the sensitizing dye in the photopolymerizable composition is from 100: 0 to 1:99, preferably from 9:99 to 1:99.
0:10 to 10:90, most preferably 80: 2
0:20:80. When the co-sensitizer is used, it is suitably used in an amount of 0.01 to 50 parts by weight, more preferably 0.02 to 50 parts by weight, based on 1 part by weight of the photopolymerization initiator.
20 parts by weight, most preferably 0.05 to 10 parts by weight.

[Linear Organic High Polymer] The photosensitive layer of the photopolymerizable lithographic printing plate of the present invention preferably contains a linear organic high 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 an addition polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615.
No., JP-B-54-34327, JP-B-58-1257
7, JP-B-54-25957, JP-A-54-927
No. 23, JP-A-59-53836, JP-A-59-71
048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is. 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, alcohol-soluble polyamide or 2,2-bis- (4
-Hydroxyphenyl) -propane and epichlorohydrin polyether are also useful.

Any of these linear organic high molecular weight polymers can be incorporated in the entire photosensitive layer composition. However, when the amount exceeds 90% by weight based on the weight of all components of the photosensitive layer composition, a favorable result is not obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

Polymerization Inhibitor In the present invention, in addition to the above basic components, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the photopolymerizable photosensitive layer composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent the polymerization. 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 addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% by weight based on the weight of the whole composition. 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 0.1% of the total composition.
5% to 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 added. 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, it is possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support and for improving the development and removability of the unexposed photosensitive 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 photosensitive layer 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, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene 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,
Examples include dimethyl sulfoxide, γ-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 coating amount of the photosensitive layer on the support mainly affects the sensitivity, developability of the photosensitive layer, and the strength and printing durability of the exposed film, and it is desirable to appropriately select the amount according to 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" To obtain the photopolymerizable lithographic printing plate of the present invention, the above-mentioned photosensitive layer is provided on an aluminum support. As the aluminum support, a conventionally known aluminum support used for a lithographic printing plate can be used without limitation. The aluminum support to be used is preferably a dimensionally stable plate-like material, and the surface thereof may be imparted with hydrophilicity, if necessary, or a known physical or chemical material suitable for the purpose of improving strength. May be applied.

Suitable aluminum supports 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,
It is preferably 0.15 mm to 0.4 mm, particularly preferably 0.1 mm to 0.4 mm.
It is 2 mm to 0.3 mm.

The aluminum support is subjected to surface treatment such as surface roughening (graining), immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation. Is preferred. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. 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. Also,
As an electrochemical surface roughening method, there is a method in which an alternating current or a direct current is used 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.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Furthermore, 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.

As another preferred example, there can be mentioned a support having a water-resistant hydrophilic layer as a surface layer on an arbitrary support. As such a surface layer, for example, US3
No. 055295, a layer composed of 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 photopolymerizable lithographic printing plate of the present invention, a protective layer can be further provided on the photosensitive layer since exposure is usually performed in the air. The protective layer is
A low-molecular compound such as a basic substance present in the atmosphere, which inhibits an image forming reaction caused by exposure in the photosensitive layer, is prevented from being mixed into the photosensitive layer, thereby enabling 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 the developing step after exposure.
Such a device for the protective layer has been conventionally devised, and is disclosed in U.S. Pat.
No. 9729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity may be used. Water-soluble polymers such as acrylic acid are known, and among these,
The 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 may have another copolymer component. As specific examples of polyvinyl alcohol, 71 to
100 mol% is hydrolyzed, and those having a molecular weight in the range of 300 to 2400 in weight average molecular weight can be mentioned. Specifically, Kuraray's PVA-105,
PVA-110, PVA-117, PVA-117H,
PVA-120, PVA-124, PVA-124H,
PVA-CS, PVA-CST, PVA-HC, PVA
-203, PVA-204, PVA-205, PVA-
210, PVA-217, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224E, PVA-405, PV
A-420, PVA-613, 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 property, 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.

The photopolymerizable lithographic printing plate of the present invention is usually subjected to image exposure and then removing the unexposed portion of the photosensitive layer with a developing solution.
Get an image. Preferable developers for use in the preparation of lithographic printing plates from these photopolymerizable lithographic printing plates include those described in JP-B-57-7427, such as sodium silicate and silicate. Potassium, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of such an inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is 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.

In addition, 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 Patent Application Laid-Open
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 addition, as a process for making a lithographic printing plate from the photopolymerizable lithographic printing plate of the present invention, the entire surface may be heated before exposure, during exposure, or between exposure and development, if necessary. . 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. Further, for the purpose of improving image strength and printing durability, it is also effective to post-heat or expose the entire surface of the developed image. 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, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur. The exposure method for the photopolymerizable lithographic printing plate of the present invention,
Known methods can be used without 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) Among them, an AlGaInN semiconductor laser (commercially available In
A GaN-based semiconductor laser (400 to 410 nm, 5 to 30 mW) is suitable in terms of wavelength characteristics and cost.

Other available light sources of 450 nm to 700 nm include Ar + laser- (488 nm), YAG
-SHG laser (532 nm), He-Ne laser (633 nm), He-Cd laser, red semiconductor laser (650-690 nm), and 700 nm-120
A semiconductor laser (800
850 nm), Nd-YAG laser (1064 nm)
Can be suitably used. Other high-pressure, high-pressure, medium-pressure, and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, and ultraviolet laser lamps (A
rF excimer laser, KrF excimer laser, etc.), and as the radiation, electron beam, X-ray, ion beam, far infrared ray, etc. can be used.
m or more laser light sources are 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.

[0242]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

(Preparation of Support) An aluminum plate having a thickness of 0.3 mm was etched by immersion in 10% by weight of sodium hydroxide at 60 ° C. for 25 seconds, washed with running water and then washed with 20% by weight.
It was neutralized and washed with nitric acid, and then washed with water. This was subjected to electrolytic surface roughening treatment in a 1% by weight nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode electricity of 300 coulomb / dm ² .
Subsequently, the mixture was placed in a 1% by weight aqueous sodium hydroxide solution at 40 ° C.
Immersion in 30% by weight sulfuric acid aqueous solution
After desmutting at 0 ° C. for 40 seconds, anodizing was performed for 2 minutes in a 20% by weight aqueous sulfuric acid solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodic oxide film was 2.7 g / m ² . The surface roughness was measured to be 0.3 μm (J
Ra display according to IS B0601).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater,
The support was then provided with a back coat layer having an applied amount of 70 mg / m ² after drying.

Sol-gel reaction liquid Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

When the above components were mixed and stirred, exotherm started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a back coat coating solution.

Pyrogallol formaldehyde condensation resin (molecular weight: 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant (N-butyl perfluorooctane 0.7 parts by weight) Sulfonamide ethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 2 10,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by weight) 50 parts by weight Methanol 800 parts by weight

(Preparation of photosensitive layer) A solution for forming a photosensitive layer having the following composition was applied on the aluminum plate treated in this manner so that the dry coating amount was 1.5 g / m ² ,
After drying for a minute, a photosensitive layer was formed.

(Sensitive layer forming solution) 0.25 g of photopolymerization initiator [X] in Table 7 below 0.2 g of sensitizing dye [Y] in Table 7 below 0.2 g of polymer binder [Z] of Table 7 below 2.0 g Polymerizable compound [R] in Table 7 below 1.6 g Additive [S] in Table 7 below 0.22 g Fluorosurfactant 0.03 g (Mechanical Fac F-177: Dainippon Ink Chemical Industry Co., Ltd.) Thermal polymerization inhibitor 0.01 g N-nitrosophenylhydroxylamici aluminum salt Pigment dispersion 2.0 g Composition of pigment dispersion Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer Combined 10 parts by weight (copolymerization molar ratio 83/17) Cyclohexanone 15 parts by weight Methoxypropyl acetate 20 parts by weight Propylene glycol monomethyl ether 40 parts by weight Methyl ethyl ketone 20 g Pro Glycol monomethyl ether 20 g

(Adjustment of Protective Layer) Polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 550) was formed on the above-mentioned photosensitive layer.
Was applied so that the dry coating weight was 2 g / m ^2, and dried at 100 ° C. for 2 minutes to produce a photopolymerizable lithographic printing plate (sensitive material) shown in Table 7 below.

[0251]

[Table 17]

The photopolymerization initiator [X], sensitizing dye [Y], polymer binder [Z], polymerizable compound [R], and additive [S] used in the photosensitive layer are shown below.

[0253]

Embedded image

[0254]

Embedded image

[0255]

Embedded image

[0256]

[Table 18]

(Evaluation of Sensitivity) The sensitizing materials thus obtained were subjected to sensitivity evaluation using different light sources according to the exposure wavelengths shown in Table 7 above. That is, a 400 nm semiconductor laser, a 532 nm FD-YAG laser,
Exposure was performed in the air using an 830 nm semiconductor laser. Each exposed light-sensitive material was added to a developer having the following composition at 25 ° C.
Immersion was performed for 10 seconds, development was performed, and the sensitivity under each exposure condition was calculated in mJ / cm ² from the minimum exposure amount at which an image was formed. The smaller the value, the higher the sensitivity. However, if the wavelength of the light source is different, the amount of energy per photon is different. Therefore, even if it is simply considered, the shorter the wavelength is, the more sensitive it is to be able to sensitize even if the above exposure amount is smaller. Becomes Therefore, Table 8 below is meaningless for comparing the sensitivity under different exposure conditions, and is merely to see the difference between the example and the comparative example under the same exposure condition. The results are shown in Table 8 below. (Composition of developer) DP-4 (Fuji Photo Film Co., Ltd.) 65.0 g Water 880.0 g Lipomin LA (20% aqueous solution, manufactured by Lion Corporation) 50.0 g

(Evaluation of Storage Stability) The above-mentioned photosensitive material before laser exposure was left under high-temperature conditions (60 ° C.) for 3 days, and thereafter, the photosensitive material after storage was exposed to laser in the same manner as described above to perform recording. The energy amount was calculated, and the energy ratio before and after high-temperature storage (energy after high-temperature storage / energy before high-temperature storage) was determined. It is preferable in terms of production that the energy ratio is 1.1 or less, and it can be said that storage stability is also good. The evaluation results are also shown in Table 8 below. (Brightroom Stability) The sensitivity is evaluated after exposing the above coated photographic material to a fluorescent lamp at 200 lux for 30 minutes to yellow or yellow-orange light with a filter capable of cutting OD6 or more and 450 nm or less. A change in sensitivity of 1.0 to 1.1 times in sensitivity ratio is allowed. The results are shown in Table 8 below.

[0259]

[Table 19]

From Table 8 above, it can be seen that the photopolymerizable lithographic printing plate of the present invention has high sensitivity and very good storage stability. In the 400 nm and 830 nm exposure systems, the bright room is further improved.

[0261]

The photopolymerizable lithographic printing plate of the present invention contains two types of polymerizable compounds, an aliphatic polymerizable compound and an aromatic polymerizable compound. In this case, the compatibility in the photosensitive layer is good, and even when a photopolymerization initiator containing four or more aromatic rings in the molecule is used, good compatibility is exhibited. Stability and light room handling can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/038 G03F 7/038 F term (Reference) 2H025 AA00 AA01 AB03 AC01 AC08 AD01 BC31 BC51 BC83 CA01 CA14 CA18 CA28 CA39 CA43 CA50 DA18 FA03 FA17 2H096 AA00 AA08 BA05 BA06 BA20 CA20 EA02 EA04 GA08 4J011 QA02 QA03 QA06 QA13 QA17 QA18 QA22 QA23 QA24 QA32 QA33 QA35 QA39 QA45 QA46 QB15 QB16 SA871 SABSA

Claims (2)

[Claims] 1. A photopolymerizable composition comprising, on an aluminum support, a photosensitive layer containing a photopolymerization initiator and two kinds of polymerizable compounds, an aliphatic polymerizable compound and an aromatic polymerizable compound. Lithographic printing plate. 2. The photopolymerizable lithographic printing plate according to claim 1, wherein the photopolymerization initiator is an initiator containing four or more aromatic rings in a molecule.