JP2001290267A - Photopolymerizable composition, photosensitive planographic printing plate and method for producing printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition excellent in sensitivity and fastness and a photosensitive planographic printing plate. SOLUTION: In the photopolymerizable composition containing an ethylenic monomer and a photopolymerization initiating system, a urethane compound (C) having >=4 urethane bonds and >=8 addition polymerizable double bonds in one molecule is contained as the ethylenic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition, and further relates to a photosensitive lithographic printing plate, a copper etching resist for wiring boards, a copper etching resist for gravure, a dry film, a color filter, and a plasma. The present invention relates to a high-sensitivity photopolymerizable composition and a photosensitive lithographic printing plate which can be used for various pattern forming materials such as a pigment dispersion resist for a display, and a method of making a printing plate.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known. For example, a photopolymerizable composition layer composed of a compound containing an addition-polymerizable ethylenic double bond and a photopolymerization initiator, and a photopolymerizable composition containing an organic polymer binder as needed. A method for forming a cured relief image by exposing a desired image to a provided photosensitive material, polymerizing and curing an exposed portion, and dissolving and removing an unexposed portion is a method of forming a cured relief image between two support members, at least one of which is transparent. A method for forming an image by exposing the light-sensitive material provided with a layer of the polymerizable composition to the transparent support to cause a change in the adhesive strength by light and peeling off the support, and other methods for forming the photopolymerizable composition layer There is an image creation method using a change in toner adhesion due to light.

Various types of photopolymerization initiation systems for such photopolymerizable compositions are known, for example, a combination of titanocenes and a sensitizer (for example, JP-A-4-219756).
Publications), a system of a pyromethene complex sensitizer and a radical generator (JP-A-4-241338, JP-A-7-5885,
Japanese Patent Application Laid-Open No. 7-225474) is known as one having relatively high sensitivity. However, all of the above photopolymerizable compositions are desired to be further improved in terms of sensitivity. For example, when an image is recorded at a high speed with a low-output argon laser or FD-YAG laser, the photopolymerizable composition has a higher sensitivity. It must be a sensitive composition.

On the other hand, it is known to use various acrylate compounds as a polymerizable component of a photopolymerizable composition. An acrylate compound which is an ester of a hydroxyl group-containing compound and (meth) acrylic acid, and a diisocyanate compound are known. A urethane acrylate compound obtained by reacting a compound containing a hydroxyl group and an acrylate group is known (for example, JP-A-11-271969).

[0005]

However, according to the study of the present inventor, in the case where it is intended to achieve higher sensitivity using a conventional urethane acrylate compound,
When a layer composed of a photopolymerizable composition is applied on a support and stacked, the composition may move under a load, or the tackiness of the photosensitive layer surface may cause a problem in productivity due to strong tackiness. understood. The present invention has been made based on the above findings, and has high sensitivity, a layer made of a photopolymerizable composition is robust (no deterioration of the photosensitive layer due to deposition), and photopolymerization having excellent productivity. An object of the present invention is to provide a composition and a photosensitive lithographic printing plate using the composition.

[0006]

According to the study of the present inventors, a specific compound as a urethane compound, namely, a specific compound,
(C) a urethane compound having four or more urethane bonds and four or more addition-polymerizable double bonds in one molecule, more specifically, (A) four active isocyanate groups in one molecule By using a urethane-based compound synthesized from a compound having the above and (B) a compound having one or more hydroxyl groups and two or more ethylenic double bonds in one molecule as a raw material, a photopolymerizable composition is obtained. The inventors have found that a layer comprising the photopolymerizable composition becomes robust while maintaining sensitivity, and arrived at the present invention. That is, the gist of the present invention is that, in a photopolymerizable composition containing an ethylenic monomer and a photopolymerization initiation system, four or more urethane bonds and four or more A photopolymerizable composition characterized by containing a urethane compound (C) having an addition-polymerizable double bond. Another aspect of the present invention resides in a photosensitive lithographic printing plate having a layer comprising the photopolymerizable composition on a support. Further, another gist of the present invention is to provide a photosensitive lithographic printing plate, after imagewise exposing the photosensitive layer to an image by exposing the image with a laser beam, and then exposing the unexposed portion of the layer composed of the photopolymerizable composition. A method for forming a photocurable photosensitive image by removing from a support, wherein the unexposed portion of the photosensitive layer is removed from the support by developing with an alkali developing solution after image exposure. It depends on the plate making method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The addition-polymerizable ethylenic double bond-containing compound (hereinafter abbreviated as “ethylenic monomer”) in the photopolymerizable composition of the present invention is, when the photopolymerizable composition is irradiated with actinic rays, It is a monomer having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation system, which is the second essential component. In the present invention, the meaning of the monomer is a concept corresponding to a so-called polymer, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer. It is.

The photopolymerizable composition of the present invention comprises, as an ethylenic monomer, (C) four or more urethane bonds per molecule.
It is characterized by containing [-NH- (C = O) -O-] and a urethane compound having four or more addition-polymerizable double bonds. The method for producing the urethane compound is not particularly limited. However, since a urethane bond can be easily formed by an addition reaction between an isocyanate group and a hydroxyl group, (A) a compound having four or more isocyanate groups in one molecule is preferably used. , (B) by reacting one or more hydroxyl groups and two or more compounds having an addition-polymerizable double bond in one molecule. 4 of the compound (A) per molecule
As a compound containing one or more isocyanate groups,
For example, a compound having four or more isocyanate groups introduced by a reaction between a compound having two or more alcoholic hydroxyl groups (hereinafter, referred to as polyhydric alcohols) and a compound having two or more isocyanate groups is exemplified.

Specifically, compounds having four or more alcoholic hydroxyl groups in one molecule such as pentaerythritol and polyglycerin are added to diisocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and trimethylhexamethylene diisocyanate. A compound containing two or more alcoholic hydroxyl groups in one molecule, such as ethylene glycol, and Duranate 24A-100, 22A-75PX, 2 manufactured by Asahi Kasei Corporation.
Biuret type such as 1S-75E, 18H-70B;
P-301-75E, E-402-90T, E-405
Compounds obtained by reacting a compound containing at least three or more isocyanate groups in one molecule such as an adduct type such as -80T are exemplified.

Further, a compound having an average of four or more isocyanate groups in one molecule can be obtained by copolymerizing isocyanateethyl methacrylate alone or with other components. Specific examples of the compound (A) include, for example, Duranate ME20-100 (trade name, manufactured by Asahi Kasei Corporation). The number of isocyanate groups in the compound (A) is preferably 6 or more, particularly preferably 7 or more. When the number of isocyanate groups is less than 4, sensitivity is inferior. The upper limit is not particularly limited, but if it is too large, it is difficult to synthesize, so it is preferably 20 or less. The number of isocyanate groups can be adjusted by the number of hydroxyl groups in the polyhydric alcohol and the type and compounding ratio of the compound having two or more isocyanate groups.

The compound (A) preferably has no ability to form a film. Specifically, the compound (A) is preferably liquid at normal temperature and normal pressure. The molecular weight of the compound (A) is usually at least 500, preferably at least 1,000, and at most 50,000,
Preferably it is 10,000 or less. If it is out of this range, the sensitivity may be reduced. The compound (A) preferably does not have an isocyanurate skeleton in its structure in terms of sensitivity and developability.

The compound (B) having one or more hydroxyl groups and two or more double bonds capable of addition polymerization in one molecule is, for example, a compound having a plurality of alcoholic hydroxyl groups such as polyhydric alcohols. A compound obtained by an esterification reaction between a compound and a compound containing a carboxyl group and a (meth) acryloyl group, wherein the compound has at least one alcoholic hydroxyl group, that is, at least one alcoholic hydroxyl group remains. A reaction product obtained by reacting the above-mentioned carboxyl group-containing compound in a ratio is exemplified. More specifically, a compound obtained by reacting 3 mol of acrylic acid with 1 mol of pentaerythritol, a compound obtained by reacting 2 mol of acrylic acid with 1 mol of pentaerythritol, and a reaction obtained by reacting 5 mol of acrylic acid with 1 mol of dipentaerythritol Compound, a hydroxyl group-containing polyfunctional acrylate compound which is an ester of polyhydric alcohols such as a compound obtained by reacting 4 mol of acrylic acid with 1 mol of dipentaerythritol and acrylic acid and has one or more alcoholic hydroxyl groups, Specific compounds include pentaerythritol triacrylate, pentaerythritol diacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate. There is. These compounds may be used alone or in a mixture.

Another example of the compound of the component (B) is a compound containing an epoxy group such as glycidyl methyl ether and at least one carboxyl group and at least one addition polymerizable double bond. Reactant with a compound having a bond; or reaction of a compound having at least one or more epoxy groups and at least one or more addition-polymerizable double bonds simultaneously with a compound having at least one or more carboxyl groups Or a compound having at least one or more carboxyl groups and at least one or more addition-polymerizable double bonds, and having at least one or more epoxy groups and at least one or more addition-polymerizable double bonds Reactants with compounds; For example, a reaction product of glycidyl methacrylate and (meth) acrylic acid is exemplified as this example).

The compound (B) preferably has three or more double bonds capable of addition polymerization, from the viewpoint of sensitivity. The reaction between the compound (A) and the compound (B), that is, the reaction between the isocyanate group of the compound (A) and the hydroxyl group of the compound (B) to obtain the urethane compound (C) should be performed according to a known method. Can be done. Specifically, the reaction is performed by reacting an isocyanate group of the compound (A) with a hydroxyl group of the compound (B) at a ratio of 1/10 to 10,
For example, a method in which both are diluted in an organic solvent such as toluene or ethyl acetate and then heated at 10 to 150 ° C. for about 5 minutes to 30 hours; or a method in which a catalyst such as n-butyltin dilaurate is added in a catalytic amount; A method in which the compound (B) is diluted with an appropriate organic solvent, and the compound (A) is sequentially added dropwise thereto later; or vice versa.

In producing the urethane compound (C), a functional group other than a double bond capable of addition polymerization may be introduced for the purpose of controlling various properties of the photopolymerizable composition.
For example, a compound (D) having a hydroxyl group and a carboxyl group in one molecule is used in combination with a compound (B) to give a compound (A)
The compound having four or more urethane bonds in one molecule, a double bond capable of addition polymerization and a carboxyl group can be obtained. More specifically,
Compound having four isocyanate groups in one molecule (A
1), a compound (B1) having one hydroxyl group and two addition-polymerizable double bonds in one molecule, and a compound (D) having one hydroxyl group and one carboxyl group in one molecule.
When 1) is reacted at a molar ratio of A1: B1: D1 of 1: 3: 1, one molecule has four urethane bonds, an average of six double bonds and one carboxyl group. Can be produced.

As the compound (D) (compound having a hydroxyl group and a carboxyl group in one molecule) which can be reacted with the compound (A) in combination with the compound (B), specifically, for example, 2-hydroxyoctane Preferred are aliphatic carboxylic acids having a hydroxyl group such as acids, 2-hydroxyhexanoic acid, 2-hydroxydecanoic acid, 3-hydroxyoctanoic acid, and 8-hydroxyoctanoic acid. Among them, carbons having a hydroxyl group at the α-position of the carboxylic acid are preferable. Carboxylic acids of numbers 4 to 20 are preferred.

The molecular weight of the urethane compound (C) is preferably from 600 to 100,000. If it is less than 600, the layer (uncured film) composed of the photopolymerizable composition tends to be inferior in terms of fastness, and if it is more than 100,000, it is disadvantageous in terms of easy synthesis and availability. The molecular weight can be determined by adjusting the types of the compounds (A) and (B) and the esterification rate. The urethane compound (C) has four or more double bonds capable of addition polymerization, preferably six or more, and more preferably eight or more, from the viewpoint of the sensitivity of the photopolymerizable composition. As the urethane compound (C), a specific urethane compound represented by the following general formula (I) is preferable.

[0018]

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[In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, and Ra has a repeating unit derived from alkyleneoxy or aryleneoxy. And an oxy group capable of bonding to Rb is 4 to 20.
Rb and Rc independently represent a C1-10 alkylene group, and Rd represents a (meth) acryl group of 1 to
R, Rb, Rc, R
d may each independently have a substituent. ]

In the formula, the alkyleneoxy group used in the repeating unit of Ra is an alkyleneoxy residue such as glycerin, pentaerythritol, and propylenetriol. The aryleneoxy group used in the repeating unit of Ra is pyrogallol. And phenoxy residues such as 1,3,5-benzenetriol. x represents an integer of 4 to 15, y represents an integer of 1 to 10, z represents an integer of 1 to 10, Ra and Rc independently represent a C1-5 alkylene group, and Rd represents a (meth) acryl group of 1 to Those representing seven organic residues are preferred. More preferably, Ra is

[0021]

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(Where k is 2 to 10), and Rb, R
c -C ₂ H ₄ to separate _{-, - CH 2 C (CH} 3) -, or,
—C ₃ H ₆ —, and Rd is

[0023]

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## EQU1 ## The proportion of the urethane compound (C) in the ethylenic monomer is usually 5 to 100% by weight, preferably 10 to 100% by weight. The urethane compound (C) may be used alone or in a mixture. In particular, when the raw material of the urethane compound is a mixture, the urethane compound (C) uses a reactant in the mixture.

Examples of the ethylenic monomer other than the urethane-based compound include a compound having one ethylenic double bond in one molecule and a polyfunctional ethylenic compound having two or more ethylenic double bonds in one molecule. Examples of the former include (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, a carboxylic acid compound having one ethylenically unsaturated bond, and ) Monoesters of dihydric alcohols and the like. When an ethylenic monomer other than urethane is used in combination, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; aliphatic polyhydroxy compounds, aromatic Esters obtained by an esterification reaction of a polyhydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polycarboxylic acid are exemplified.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate glycerol acrylate, and the like. Methacrylate S in which the acrylate of the exemplified compound is replaced with methacrylate Le similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced Kuroneto.

Examples of the ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. And methacrylic acid esters. The ester obtained by the esterification reaction of the unsaturated carboxylic acid and the polycarboxylic acid and the polyhydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid, and ethylene glycol. Examples include condensates, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

Other examples of the polyfunctional ethylenic monomer used in the present invention include urethane acrylates such as an addition reaction product of tolylene diisocyanate and hydroxyethyl acrylate; addition of a diepoxy compound and hydroxyethyl acrylate Epoxy acrylates such as reactants; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate;
A vinyl group-containing compound such as divinyl phthalate is useful. In the present invention, as the ethylenic monomer used in combination with the urethane compound (C), a phosphate compound containing at least one (meth) acryloyl group is particularly preferable. Although not particularly limited, specific examples include compounds represented by the following general formulas (II) and (III).

[0029]

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(In the general formulas (II) and (III), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 1 to 25, and m represents an integer of 1 to 3.) Of the compounds represented by II) and (III), n
Is preferably 1 to 10 from the viewpoint of improving the printing durability and the removability of the non-image area. Among the compounds represented by the general formulas (II) and (III), specific examples of particularly preferable compounds include methacryloxyethyl phosphate, bis (methacryloxyethyl) phosphate, and methacryloxyethylene glycol phosphate. And the like. The phosphate compound used in the present invention may be a single compound or a mixture of a plurality of compounds. The content of the ethylenic monomer other than the urethane compound (C) is 0 to 95% by weight, preferably 0 to 90% by weight in the ethylenic monomer.

Next, the photopolymerization initiation system used when used as a photopolymerizable composition will be described. The photopolymerization initiation system is usually composed of a radical generator and a sensitizer, and optionally contains a polymerization accelerator. As the radical generator, any of those capable of initiating the polymerization of the ethylenic monomer can be used. Among them, examples of a radical generator that generates an active radical by interacting with a photoexcited sensitizer to produce an active radical include, for example, titanocenes, hexaarylbiimidazoles, organic boron anions (borates), and halogenated carbons. Hydrogen derivatives (halomethyl group-containing compounds), diaryliodonium salts, organic peroxides, and the like can be given.

As the titanocenes, for example, JP-A-59
And the like. Any of various titanocenes described in JP-A-152396 and JP-A-61-151197 can be appropriately used. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-
Bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,
6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-
Di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis -2,6-difluorophenyl-1-
Yl, di-cyclopentadienyl-Ti-bis-2,6
-Difluoro-3- (pyr-1-yl) -phenyl-1-
Titanocene compounds having a dicyclopentadienyl group such as yl can be mentioned. These may be used in combination of two or more.

The hexaarylbiimidazoles include, for example, 2,2′-bis (o-chlorophenyl)-
4,4 ', 5,5'-tetra (p-fluorophenyl)
Biimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-iodophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-Tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4'5,5'-tetra (p-chlorophenyl) biimidazole , 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-
p-methoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole,
2'-bis (o-chlorophenyl) -4,4'5,5 '
-Tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4 '
5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4′5,5′-tetra (o, p-di Hexaarylbiimidazoles having a halogen substituent on the benzene ring such as (chlorophenyl) biimidazoles are preferred.

These hexaarylbiimidazoles can be used in combination with various kinds of biimidazoles, if necessary. Biimidazoles are, for example, Bul
l. Chem. Soc. Japan. 33,565 (1
960) and J.M. Org. Chem. 36 [16] 22
62 (1971).

Examples of the organic boron anion include, for example, JP-A-62-143044 and JP-A-62-150242.
JP-A-9-188865, JP-A-9-18868
6, JP-A-9-188710, and Patent No. 276476.
9 and Kunz, Martin "Rad Tech'98.Pr
Oceding April 19-22, 1998, Chicago "and the like, and particularly preferably those represented by the following general formula (IV).

[0036]

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[In the formula (IV), R ² , R ³ , R ⁴ and R ⁵
Are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A good aryl group or a heterocyclic group is shown, which may be linked to each other to form a cyclic structure, and at least one of them is an alkyl group which may have a substituent. ]

Here, when R ² , R ³ , R ⁴ and R ⁵ in the formula (IV) are alkyl groups, the number of carbon atoms is usually from 1 to 1.
5, preferably 1 to 5, the number of carbon atoms when it is an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5,
When it is an aryl group, it usually has 6 to 20, preferably 6 to 15, and when it is a heterocyclic group, it usually has 4 to 4 carbon atoms.
20, preferably 4 to 15, and examples of the substituent therefor include a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, and a trimethylsilyl group. Among them, R ^{2 to} R ⁴ are independently a phenyl group optionally substituted with a halogen atom, and R ⁵ has 1 carbon atom.
It is preferably an alkyl group of from 6 to 6.

As these organic boron anions, specifically, for example, n-butyl-methyl-diphenylboron, n-butyl-triphenylboron,
-Butyl-tris (2,4,6-trimethylphenyl)
Boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-
Fluorophenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3 , 4,5,6
-Pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (trifluoromethyl) boron anion, n
-Butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion;

Examples of counter cations include onium compounds such as alkali metal cations, ammonium cations, phosphonium cations, sulfonium cations, and iodonium cations, and pyrylium cations, thiapyrylium cations, and indolium cations. However, an organic ammonium cation such as a tetraalkylammonium is preferable, and in particular, has 1 to 6 carbon atoms.
The tetraalkylammonium cation of the alkyl group is preferred.

Examples of the halomethyl group-containing compound include mono,
An s-triazine compound in which a di- or trihalogen-substituted methyl group is bonded to an s-triazine ring is preferable, and a compound represented by the following general formula (V) is particularly preferable.

[0042]

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[In the formula (V), X represents a halogen atom,
W represents an aryl group or a heterocyclic group which may have a substituent, and R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group,
Or an aryl group, and r is an integer of 0-2. ]

These s-triazine compounds include:
Specifically, for example, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-
4,6-bis (trichloromethyl) -s-triazine,
2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-chlorophenyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
[1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-tolyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (4-methoxynaphthyl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
Phenylthio-4,6-bis (trichloromethyl) -s
-Triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6
-Bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like, among which 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 , 4-Epoxyphenyl) -4,6-bis (trichloromethyl)
-S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl)-
4,6-bis (trichloromethyl) -s-triazine and the like are preferable because of excellent stability over time.

These radical generators can be appropriately selected and used depending on the exposure wavelength. For example, when the exposure wavelength is in the range of 350 to 650 nm, titanocenes and / or
Alternatively, the use of hexaarylbiimidazoles is particularly preferable because sensitivity, storage stability, adhesion to a coating film base, and the like are particularly good. When the exposure wavelength is 650 to 1300 nm, the use of an organic boron anion and / or a halomethyl group-containing compound is particularly preferred because sensitivity, preservability, adhesion to a coating film base, and the like are particularly good. Next, the sensitizer among the photopolymerization initiators will be described. The sensitizer in the present invention,
It means a compound capable of effectively generating an active radical upon irradiation with light when coexisting with the above-mentioned activator.

Examples of typical sensitizers include triphenylmethane-based leuco dyes such as leuco crystal violet and leucomalachite green disclosed in US Pat. No. 3,479,185, and erythrosine. Photoreducing dyes such as Eosin Y and US Pat. No. 3,549,367; US Pat.
Aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat.
The β-type disclosed in U.S. Pat. No. 3,844,790.
Diketones, indanones described in U.S. Pat. No. 4,162,162, ketocoumarins described in JP-A-52-112681, and JP-A-59-56403.
No. 4,594,3, disclosed in US Pat. No. 4,594,311.
No. 10, aminophenyl heterocycles, U.S. Pat. No. 4,966,830, julolidine heterocycles, pyromethene dyes described in JP-A-5-241338, other cyanine dyes, And dialkylbenzene compounds.

These sensitizers can be appropriately selected and used depending on the exposure wavelength.
If m, a dialkylbenzene-based compound is preferable,
If the exposure wavelength is 400 to 650 nm, ketocoumarins and pyromethene dyes are preferred, and the exposure wavelength is 650.
If it is 〜1300 nm, a cyanine dye is preferred.

The dialkylaminobenzene-based compound has a dialkylaminobenzene structure and may have any substituent. Among them, the dialkylaminobenzophenone-based compound and p-amino group on the benzene ring Dialkylaminobenzene compounds having an aromatic heterocyclic group as a substituent at the carbon atom at the 1-position, and the alkyl groups constituting the dialkylamino group of these compounds are bonded to each other, and / or the alkyl group is located on the benzene ring. And a compound having a structure in which a nitrogen-containing heterocyclic structure is formed by bonding to a carbon atom adjacent to the carbon atom to which the amino group is bonded. In the above, the amino groups constituting the dialkylamino group may be the same or different, and preferably have 1 to 6 carbon atoms.

Among them, preferred dialkylaminobenzene compounds are represented by the following formulas (VI) and (VII).

[0050]

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[0051] (In the formula (VI), R ⁷ ~R ¹⁰ are each independently an alkyl group having 1 to 6 carbon atoms, R ¹¹ to R
¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, wherein R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ⁷ and R ¹¹ , R ⁸ and R ¹² , R ⁹
And R ¹³ and R ¹⁰ and R ¹⁴ may be independently bonded to each other to form a ring. )

[0052]

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(In the formula (VII), R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms, and R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. To Q
Is an oxygen atom, a sulfur atom, a dialkylmethine group, or-
N (R ¹⁹ ) —, wherein R ¹⁹ is a hydrogen atom or carbon 1-6
Represents an alkyl group. However, R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ may be independently bonded to form a ring. ) The alkyl group of the dialkylmethylene has 1 to 6 carbon atoms, preferably 1. Formulas (VI) and (VI
When any one of R ^{7 to} R ¹⁸ in I) is bonded to form a ring, the ring is preferably a 5- or 6-membered ring, particularly preferably a 6-membered ring. As the compound represented by the formula (VI),
4,4'-dimethylaminobenzophenone, 4,4'-
Examples include diethylaminobenzophenone and compounds having the following structure.

[0054]

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The compounds represented by the general formula (V) include 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, and 2- (p-dimethylaminophenyl) Benzo [4,5] benzoxazole, 2- (p-
Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylamino Phenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole and compounds having the following structure.

[0056]

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The cyanine dye has a basic structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is bonded by a polymethine (-CH =) n chain. A so-called cyanine-based dye in a broad sense having a structure in which atoms form a heterocycle and a heterocycle is bonded via a polymethine chain as a basic structure, specifically, for example, quinoline-based (so-called cyanine-based), indole-based (So-called indocyanine-based), benzothiazole-based (so-called thiocyanine-based), pyrylium-based, thiapyrylium-based, squarylium-based, croconium-based, azurenium-based, etc., and an acyclic heteroatom bonded through a polymethine chain Examples include a so-called polymethine dye having a structure, and among them, an indole dye and a benzothiazole dye are preferable. As the indole-based and benzothiazole-based dyes, those represented by the following general formula (VIII) are particularly preferable.

[0058]

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[In the formula (VIII), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom;
²⁰ and R ²¹ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent,
An alkynyl group which may have a substituent or a phenyl group which may have a substituent is shown, and a penta, hepta, nona, or undecamethine group which may have an L1 substituent is shown. The two substituents on the penta, hepta, nona, or undecamethine group are linked to each other and have 5 to 7 carbon atoms.
May form a cycloalkene ring, a cycloalkeneone ring, a cycloalkenedione ring, or a cycloalkenethione ring, and the fused benzene ring may have a substituent, in which case two adjacent substituents May be connected to each other to form a fused benzene ring. Xa-represents a counter anion. ]

Here, R ²⁰ and R ²¹ in the formula (VIII)
Is an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and when it is an alkenyl group or an alkynyl group, the number of carbon atoms is usually 2 to 15, preferably 2 to 10, and a phenyl group as those substituents including, from 1 to 15 carbon atoms, preferably 1 to 10 alkoxy group, a phenoxy group, hydroxy group, or a phenyl group, examples of the substituent in L ^1, directly Or an aromatic ring or a heterocyclic ring through an ether or thioether bond, an alkyl group, an amino group, or a halogen atom, and the like.
Examples thereof include an alkyl group, an alkoxy group, a nitro group, and a halogen atom. Of these, cyanine dyes having a heterocyclic ring on L ¹ directly or via an ether or thioether bond are preferred.

Further, if necessary, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzimidazole may be used as a polymerization accelerator in the photopolymerization initiation system used in the present invention.
Mercaptobenzoxazole, 3-mercapto-1,
By adding a hydrogen-donating compound such as 2,4-triazole, N-phenylglycine and a derivative thereof, and an alkyl N, N-dialkylbenzoate, the photopolymerization initiation ability can be further enhanced. Of these, particularly preferred are those having a mercapto group such as N-phenylglycine and derivatives thereof, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 3-mercapto-1,2,4-triazole. Compounds and N, N-dialkyl benzoic acid alkyl esters.

The photopolymerizable composition of the present invention generally preferably contains a polymer binder. Specific examples of the polymer binder include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, and maleimide. Or copolymer, other, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester,
Examples thereof include polyether, polyethylene terephthalate, acetylcellulose, and polyvinyl butyral. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
(Meth) acrylic acid and at least one (meth) acrylic ester which may be substituted, such as butyl acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and benzyl (meth) acrylate; A copolymer containing a carboxyl group in a molecule contained as a copolymer component (hereinafter, referred to as a “carboxyl group-containing copolymer”) is preferable. In this specification, (meth) acryl means methacryl or acryl.

The preferred acid value of the carboxyl group-containing polymer binder is 10 to 250 KOH · mg / g, and the preferred polystyrene equivalent weight average molecular weight (hereinafter abbreviated as Mw) is 5,000 to 1,000,000. These polymer binders desirably have an unsaturated bond in a side chain, and include a resin obtained by reacting a compound having both an epoxy group and an unsaturated group with a carboxyl group-containing copolymer as described above. Examples of the compound having both an epoxy group and an unsaturated group include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, and itaconic acid Examples include aliphatic epoxy group-containing unsaturated compounds such as monoalkyl monoglycidyl ester, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, and 3,4-epoxycyclohexylmethyl (meth) acrylate. it can.

Among them, allyl glycidyl ether, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferred, and 3,4-epoxycyclohexylmethyl (meth) acrylate is more preferred. The above-mentioned resins having both a carboxyl group and a side chain double bond have a preferred molecular weight of 10,000 to 1,000,000, preferably 20
000 to 500,000. Further, the side chain double bond is 1 to 50 relative to the main chain monomer unit 100,
Preferably, 5 to 40 units are introduced. The main components of the photopolymerizable composition of the present invention have been described in detail above, but the preferred use ratio thereof is an internal sensitizer of a photopolymerization initiator based on 100 parts by weight of the ethylenic monomer. Is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight, a radical activator is preferably 0.1 to 80 parts by weight, and particularly preferably 0.5 to 6 parts by weight.
0 parts by weight, preferably 0.1 to 80 parts by weight of a polymerization accelerator, particularly preferably 0.5 to 60 parts by weight, and preferably 10 to 400 parts by weight, particularly preferably 2 to 400 parts by weight of a polymer binder.
It is in the range of 0 to 200 parts by weight.

For the purpose of improving sensitivity, the photopolymerizable composition of the present invention contains an amine compound having a pKb (dissociation constant) of 7 or less at 25 ° C. or a primitive group [N-
It preferably contains an amine compound having [CH ² ]. More preferably, pKb at 25 ° C. is contained in the photosensitive layer.
Is 7 or less, and has an atomic group [N—CH ₂ ] in the molecule. The amine may be any of an aliphatic, alicyclic or aromatic amine as long as the above conditions are satisfied, and the hydrocarbon group in the amine may have a substituent. The amine is not limited to a monoamine, and may be a polyamine such as a diamine or a triamine, or may be any of a primary amine, a secondary amine, and a tertiary amine. However, it is substantially selected from aliphatic amines having an optionally substituted hydrocarbon group in terms of pKb. The amine preferably has a pKb of 5 or less.
Further, the lower limit of pKb is preferably 3 or more. Also,
Amines having the atoms in the molecule [CH ₂ -N-CH _2] is more preferred.

Preferred amine compounds include aliphatic amines having a hydrocarbon group which may have a substituent, and specific examples include butylamine, dibutylamine, tributylamine, amylamine, diamylamine, triamylamine, and the like. Aliphatic amines which may be substituted with a hydroxyl group or a phenyl group, such as hexylamine, dihexylamine, trihexylamine benzylamine, dibenzylamine, tribenzylamine, triethanolamine, allylamine, diallylamine and triallylamine. Can be

The photopolymerizable composition of the present invention may further contain other substances depending on the purpose in addition to the above essential components. For example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol; coloring agents composed of organic or inorganic dyes and pigments; dioctyl phthalate, didodecyl phthalate, tricresyl Plasticizers such as phosphates, sensitivity property improvers such as tertiary amines and thiols, and other additives such as dye precursors can also be added. Further, the photopolymerizable composition of the present invention can contain a surfactant as a coating property improving agent. Among them, particularly preferred are fluorine-based surfactants.

The above-mentioned additives are preferably added in an amount of 2 parts by weight or less of a thermal polymerization inhibitor, 20 parts by weight or less of a coloring agent, 40 parts by weight or less of a plasticizer, and 100 parts by weight of an ethylenic monomer. The range is 30 parts by weight or less of the body and 10 parts by weight or less of the surfactant. The photopolymerizable composition described above is diluted with an appropriate solvent, applied on a support and dried to form a photosensitive layer. When used as a photosensitive lithographic printing plate, an aluminum support which has been subjected to anodizing after surface roughening can be suitably used as the support. As a method of surface roughening, generally known brush polishing method, ball polishing method,
Examples include methods such as electrolytic etching, chemical etching, liquid honing, and sand blasting, and combinations thereof, and preferably include brush polishing, ball polishing, electrolytic etching, chemical etching, and liquid honing. Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution as required. The aluminum plate thus obtained is usually subjected to anodizing treatment, and particularly preferably a method of treating with an electrolytic solution containing sulfuric acid. A method of anodizing with an electrolytic solution containing sulfuric acid is a conventionally known method, for example, Japanese Patent Application Laid-Open No.
This is performed according to the method described in JP-A-13894. Specifically, for example, sulfuric acid is 5 to 50% by weight, preferably 15% by weight.
And a temperature of about 5 to 50 ° C., preferably 15 to 35 ° C., and a current density of 1 to 60 A / dm.
² is performed in about 5 to 60 seconds. Further, if necessary, the surface is treated with an alkali silicate such as sodium silicate treatment or hot water, or immersed in an aqueous solution containing an aqueous polymer compound such as a resin having a cationic quaternary ammonium group or polyvinylphosphonic acid. Processing can be performed. The thickness of the aluminum support is usually 0.01 to 10
mm, preferably about 0.05 to 1 mm, and the surface roughness is usually 0.3 to 1.0 μm, preferably 0.4 to 0.8 μm in terms of average roughness Ra specified in JIS B0601.
It is about.

The photosensitive composition can be applied by a known method such as dip coating, coating rod, spinner coating, spray coating, roll coating and the like. The amount applied varies according to the application, the range of 0.5 to 100 g / m ² is preferable as dry coating film thickness preferably 0.5 to 5 g / m ² in the planographic printing plate. The drying temperature is, for example, about 30 to 150 ° C.
Preferably at about 40 to 110 ° C. for about 5 seconds to about 60 minutes,
Preferably, it is about 10 seconds to 30 minutes.

Further, an oxygen blocking layer can be provided on the above-mentioned photosensitive layer in order to prevent a polymerization inhibition effect by oxygen. Specific examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide,
Examples include water-soluble polymers such as cellulose. Among them, those containing polyvinyl alcohol having particularly high oxygen gas barrier properties are preferable.

In general, when the photopolymerizable composition of the present invention is used for a photosensitive lithographic printing plate, the above-mentioned oxygen barrier layer is provided on the photosensitive layer. Is used as a sensitizer, and a system using an organic boron anion and / or a halomethyl group-containing compound as a radical generator, even when there is no oxygen barrier layer due to the effect of the urethane compound compounded as an ethylenic monomer. A photosensitive lithographic printing plate in which the photosensitive layer is the uppermost layer is advantageous because it exhibits practical sensitivity. The photosensitive lithographic printing plate having the photopolymerization system usually has a wavelength of 650 to 1300 nm, preferably 700 to 1200 nm, and more preferably 800 to 1200 nm.
Irradiated by laser light of レ ー ザ ー 1100 nm.

The exposure light source applicable to the composition of the present invention is not particularly limited, but includes, for example, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, and a violet laser. , A blue laser, an argon ion laser, an FD-YAG laser, a semiconductor infrared laser, a YAG laser, and a helium neon laser can be particularly preferably used. In particular, since the photosensitive lithographic printing plate of the present invention is suitable for laser scanning exposure, it is advantageous to use a laser as a light source, for example, 410 nm of an indium gallium nitride semiconductor laser.
Around, around 488nm of argon ion laser, FD
-Around 532 nm of YAG laser, around 780 nm of semiconductor laser, around 830 nm of semiconductor laser, Y
A laser that oscillates each wavelength around 1064 nm of the AG laser is specifically exemplified.

The photopolymerizable composition of the present invention can form an image on a support by performing image exposure with such a light source and developing with an aqueous solution containing a surfactant and an alkali. . The aqueous solution may further contain an organic solvent, a buffer, a dye or a pigment. Suitable alkali agents include inorganic alkalis such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. And organic amine compounds such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine. These can be used alone or in combination. PH of alkaline developer
Is usually about 9 to 14.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters;
Anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts and the like; amphoteric surfactants such as alkyl betaines and amino acids can be used. Further, as the organic solvent, for example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like can be contained as necessary.

Further, as a support of the photosensitive lithographic printing plate, the support was subjected to a hydrophilization treatment, and the gum tape obtained by the method of measuring the peel strength with a gum tape was used to separate the support from the hydrophilic treatment support. When the peel strength is 500 g / cm or less, a plate making method in which development is performed on a printing machine without using an alkali developer can be employed. Specifically, this plate making method is to expose the photosensitive layer of a photosensitive lithographic printing plate by imagewise exposure to light-harden the photosensitive layer in an imagewise manner, and then remove the unexposed portion of the photosensitive layer from the support to obtain a light-sensitive layer. A method for forming a cured photosensitive image, comprising mounting a photopolymerizable lithographic printing plate after image exposure on a plate cylinder of a printing machine, and dampening water and printing ink on a photosensitive layer of the photopolymerizable lithographic printing plate. When the ink is transferred to the roller surface of the blanket roller to supply the unexposed portion together with the ink, the unexposed portion is transferred to the roller surface of the blanket roller by utilizing the adhesiveness of the ink. It is characterized by being removed from the support.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Synthesis Example 1 <Synthesis of urethane compound-1 by reaction of compound (A) with compound (B)> In a four-necked flask, 100 ml of ethyl acetate, 180 mg of n-butyltin dilaurate, 60 mg of paramethoxyphenol, A-9530 ( 38.6 g of a compound having dipentaerythritol pentaacrylate as a main component, having a molecular weight of about 530 (theoretical value) manufactured by Shin-Nakamura Chemical Co., Ltd. was added in order. In addition, ME20 was added so that the isocyanate group became 0.9 times the molar amount of hydroxyl group of A-9530.
-100 (manufactured by Asahi Kasei Corporation: containing an average of 9 isocyanate groups per molecule; molecular weight of about 5000) was added dropwise with stirring. After dropping, heat to 70 ° C and add IR
The reaction was continued until the peak of isocyanate disappeared. The reaction product is referred to as "urethane compound-1". (The molecular weight is about 10,000.)

Synthesis Example 2 <Synthesis of urethane compound-2 by reaction of compound (A) with compound (B)> In Synthesis Example 1, 90 ml of ethyl acetate was added to A-953.
0 to NK701A (manufactured by Shin-Nakamura Chemical Co., Ltd .: reaction product of glycidyl methacrylate and acrylic acid; theoretical molecular weight 21)
4. ) Was changed to 9.4 g, and ME20-100 was changed to N
The reaction was carried out in the same manner as in Synthesis Example 1 except that the isocyanate group was changed to be 0.9 times the molar amount of hydroxyl group of K701A, and "urethane compound-2" (molecular weight of about 7
000).

Synthesis Example 3 <Synthesis of Urethane Compound-3 by Reaction of Compound (A) and Compound (B)> In a four-necked flask, 150 ml of cyclohexanone, 180 mg of n-butyltin dilaurate, 60 mg of paramethoxyphenol, and A- 9530 (manufactured by Shin-Nakamura Chemical Co., Ltd .: compound containing dipentaerythritol pentaacrylate as a main component) 34.7 g and 2-hydroxy-n-octanoic acid 0.35 g (molecular weight: 160) were sequentially added. Thereafter, as in Synthesis Example 1, ME20-1 was added so that the isocyanate groups became 0.9 times the total molar amount of hydroxyl groups.
The reaction was carried out using the compound No. 00 to obtain "urethane compound-3" (molecular weight: about 9400).

Synthesis Example 4 <Synthesis of Polymer Binder-1> Methyl methacrylate / methacrylic acid = 80/20 m
ol% (preparation ratio) of a copolymer, Mw = 70,000 (hereinafter abbreviated as “polymer binder-1”) was synthesized. This binder
A-200 (manufactured by Daicel Chemical Industries, Inc., a compound containing an alicyclic epoxy group and an acryloyl group) was reacted with 50% of the entire methacrylic acid component 1 to obtain polymer binder-1.

Synthesis Example 5 <Synthesis of Polymer Binder-2> Vinyl methacrylate / acrylonitrile / allyl glycidyl ether methacrylate / methacrylic acid = 40 /
15/30/15 mol% (charge ratio) of copolymer, M
w = 200,000 (hereinafter abbreviated as “polymer binder-2”) was synthesized.

Examples 1 to 4 and Comparative Examples 1 and 2 <Production of aluminum support> Support-1 An aluminum plate was degreased with 3% sodium hydroxide, and the aluminum plate was degreased in a 11.5 g / l hydrochloric acid bath. ° C, 80A / dm ²
Electrolytic etching at a current density of 11 seconds, washing with water, anodizing at 30 ° C. in a 30% sulfuric acid bath at 11.5 A / dm ² for 15 seconds, washing with water, and drying to obtain an aluminum plate for a lithographic printing plate (hereinafter ““. Support-1 ").

The following photopolymerizable composition coating solution-1 was coated on the support-1 with a bar coater to obtain a dry film thickness of 2 g / m2.
Coating and drying were performed to obtain ² . Further, an aqueous solution of polyvinyl alcohol was dried thereon by using a bar coater to a dry film thickness of 3.
g / m ² to obtain a photosensitive lithographic printing plate.

[0083]

(Table 1) (Photopolymerizable composition coating liquid-1) Urethane compounds-1, -2, -3 shown in Table 1 Compounding amounts shown in Table 1 Ethylene monomer-1 shown below, -2, -3 Compounding amount shown in Table 1 The following radical generator T-15 5 parts by weight The following polymerization accelerator E-15 5 parts by weight The following polymerization accelerator E-25 5 parts by weight The following sensitizer S-1 0.5 part by weight The following sensitizer S-2 0.5 part by weight The polymer binder-1 45 parts by weight Pigment (PB15: 6) 4 parts by weight Emulgen 104P (manufactured by Kao Corporation) 2 parts by weight S-381 (fluorinated surfactant manufactured by Asahi Glass Co., Ltd.) 0.3 parts by weight Disperbyk 161 (dispersant manufactured by BYK Chemie) 2 parts by weight propylene glycol monomethyl ether acetate 600 parts by weight cyclohexanone 545 parts by weight

[0084]

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[0085]

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[0086]

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[0087]

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The following items were evaluated for the obtained photosensitive lithographic printing plate. The results are shown in Table 1. <Sensitivity evaluation> A step filter (manufactured by Konica) and a filter for completely blocking laser light were attached to a part of the obtained photosensitive lithographic printing plate, and an FD-YAG laser exposure machine (product name: Platejet. Cymbolic) was used.
Science), 4000 dpi, 6.8 m
100% under the condition of W (plate exposure amount 240 μJ / cm ² )
The image was exposed. Thereafter, the film was immersed in an aqueous solution containing 3% by weight of potassium silicate A and 5% by weight of Perex NBL (manufactured by Kao Corporation) at 25 ° C. for 30 seconds and then rubbed once with a sponge for development. After development, the highest step number that was sufficiently cured was read to evaluate the sensitivity.

<Evaluation of Deposition (Evaluation of Fastness)> Each of the obtained photosensitive lithographic printing plates was cut into 6 cm squares, and after stacking, a weight of 7 kg was applied through a 2 cm diameter column and left for 20 hours. After standing, observe the portion of each printing plate where the load was applied. ○ indicates that the photosensitive layer has hardly changed, △ indicates that the photosensitive layer has some change or trace, A mark that shows traces so that the surface is visible is marked as x.

[0090]

[Table 2]

Examples 5 to 10 <Manufacture of Aluminum Support> Support-2 An aluminum plate having a thickness of 0.2 mm was degreased with 3% sodium hydroxide, and was degreased in a 18.0 g / l hydrochloric acid bath. 25
Electrolytic etching was performed for 15 seconds at 80 ° C. and a current density of 80 A / dm ² , followed by desmutting with a 1% aqueous sodium hydroxide solution at 50 ° C. for 5 seconds, followed by neutralization with a 10% aqueous nitric acid solution at 25 ° C. for 5 seconds. After washing with water, 30 ° C in a 30% sulfuric acid bath,
Anodize under conditions of 10 A / dm ² for 16 seconds, and further 50
The resultant was immersed in an aqueous solution of ppmCMC for 5 seconds and dried to obtain an aluminum plate for a lithographic printing plate (hereinafter abbreviated as “support-2”). The formed anodized film is 2.1 g / m ² . Peel strength of Support-2 by the following measurement method was 300 g.
Met.

<Peel Strength> The peel strength of the gum tape of the hydrophilic support was measured according to the following measuring method. As shown in FIG. 1 (a), the peel strength (hereinafter, referred to as "gum tape peel strength") of the support subjected to the hydrophilic treatment (hereinafter, referred to as "hydrophilic support") by a gum tape showing surface adhesiveness is as shown in FIG. Gum tape (SLIONTEC SL)
ION TAPE) 3 at 25 ° C., 5 kg / cm ² , 50 c
After pressure bonding at a rate of m / min, the support 2 is fixed on the fixing base 2 and is necessary when the gum tape 3 and the support 1 are pulled at a distance of 30 cm per minute in the direction of 180 ° at a speed of 180 °. The linear tension (g) obtained by dividing the force F by the width of the packing tape
/ Cm).

The following photopolymerizable composition coating liquid-2 was coated on the support-2 using a bar coater to obtain a dry film thickness of 2 g / m2.
Coating and drying were performed to obtain ² . Further, an aqueous solution of polyvinyl alcohol was dried thereon by using a bar coater to a dry film thickness of 3.
The resultant was applied and dried so as to have a thickness of 3 μm at g / m ² to prepare a photosensitive lithographic printing plate. The obtained photosensitive lithographic printing plate was evaluated for sensitivity at the time of print development (the following sensitivity evaluation-2). The results are shown in Table 2.

[0094]

[Table 3] (Photopolymerizable composition coating liquid-2) 10 parts by weight of the above-mentioned ethylenic compound-1 35 parts by weight of the following urethane-based compound-4 65 parts by weight of the above-mentioned polymer binder-2 65 parts by weight Agent 1 part by weight Radical generator shown in Table 2 Compounding amount shown in Table 2 Phthalocyanine pigment 5 parts by weight Tribenzylamine 10 parts by weight Propylene glycol monomethyl ether acetate 1000 parts by weight Propylene glycol monomethyl ether 100 parts by weight

[0095]

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<Sensitivity evaluation-2> A photosensitive lithographic printing plate was subjected to a near-infrared exposure apparatus (Trendsetter 3224-
T: oscillation wavelength 830 nm), image exposure was performed at various exposure amounts, the printing plate was mounted on a plate cylinder on a printing press (Mitsubishi Heavy Industries lithographic printing press “Dia F-2”), and fountain solution (Astro) was used. No.1 mark II), printing was performed by printing 100 sheets using printing ink (Toyo Process Ink High Echo Magenta), and the minimum laser exposure amount at which the printed image on the 100th printed sheet was obtained. The sensitivity was evaluated by (energy), where F in Table 2 was 1000 mJ / c.
This shows that no image was formed even at an exposure amount of m ² .

[0097]

[Table 4]

Examples 11 to 16 <Manufacture of Aluminum Support> Support-3 An aluminum plate having a thickness of 0.2 mm was degreased with 3% sodium hydroxide, and was degreased in a 18.0 g / l hydrochloric acid bath. 25
Electrolytic etching was performed for 15 seconds at 80 ° C. and a current density of 80 A / dm ² , followed by desmutting with a 1% aqueous sodium hydroxide solution at 50 ° C. for 5 seconds, followed by neutralization with a 10% aqueous nitric acid solution at 25 ° C. for 5 seconds. After washing with water, 30 ° C in a 30% sulfuric acid bath,
Anodized for 16 seconds under the conditions of 10 A / dm ² , washed with water and dried to obtain an aluminum plate for a lithographic printing plate (hereinafter referred to as “support-
3 ”. ) Got. The formed anodized film is 2.
1 g / m ² .

The following photopolymerizable composition coating solution-3 was prepared on the support-3, and the coating solution was applied to a dry film thickness of 2 g / m ² using a bar coater and dried. did. Further, an aqueous solution of polyvinyl alcohol was applied and dried using a bar coater to a thickness of 3 μm at a dry film weight of 3 g / m ² to prepare a photosensitive lithographic printing plate.
The obtained photosensitive lithographic printing plate was evaluated for sensitivity at the time of alkali development (the following sensitivity evaluation-3). The results are shown in Table 3.

[0100]

(Table 5) (Photopolymerizable composition coating liquid-3) 10 parts by weight of the ethylenic compound-1 35 parts by weight of the urethane-based compound-4 65 parts by weight of the polymer binder-2 65 parts by weight Sensitization shown in Table 3 Agent 1 part by weight Radical generator shown in Table 3 Amount shown in Table 3 Phthalocyanine pigment 5 parts by weight Tribenzylamine 10 parts by weight Propylene glycol monomethyl ether acetate 1000 parts by weight Propylene glycol monomethyl ether 100 parts by weight

<Sensitivity Evaluation-3> A photosensitive lithographic printing plate was prepared by using a near infrared exposure apparatus (Trendsetter 3224-
(T: oscillation wavelength: 830 nm) using various exposure amounts. Next, 0.7% by weight of sodium carbonate and an anionic surfactant (Perex NB manufactured by Kao Corporation)
L) Development was carried out by immersion in an aqueous solution containing 0.5% by weight at 28 ° C. for 30 seconds. After the development, the minimum exposure energy required to give the obtained cured image was calculated.

[0102]

[Table 6]

[0103]

The photosensitive composition of the present invention is excellent in fastness while maintaining high sensitivity, so that it is excellent in handleability when used as a photosensitive lithographic printing plate, and achieves stable performance when used. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/029 G03F 7/029 7/031 7/031 7/032 7/032

Claims (19)

[Claims] In a photopolymerizable composition containing an ethylenic monomer and a photopolymerization initiation system, four or more urethane bonds and four or more addition polymerizations in one molecule as an ethylenic monomer. A photopolymerizable composition comprising a urethane compound (C) having a possible double bond. 2. The urethane compound (C) having a molecular weight of 60
The photopolymerizable composition according to claim 1, wherein the number is from 0 to 200,000. 3. The photopolymerizable composition according to claim 1, wherein the urethane compound (C) is represented by the following general formula (I). Embedded image [In the formula (I), x represents an integer of 4 to 20, y represents an integer of 0 to 15, z represents an integer of 1 to 15, Ra has a repeating unit derived from alkyleneoxy or aryleneoxy,
And Rb represents a group having 4 to 20 oxy groups capable of binding to Rb, Rb and Rc each independently represent a C1 to 10 alkylene group, and Rd represents an organic residue having 1 to 10 (meth) acryl groups. , Ra, Rb, Rc, and Rd may each independently have a substituent. ] 4. A urethane compound (C) comprising: (A) a compound having four or more isocyanate groups in one molecule;
(B) The photopolymerization according to any one of claims 1 to 3, which is obtained by reacting one or more hydroxyl groups and two or more compounds having an addition-polymerizable double bond in one molecule. Composition. 5. The photopolymerizable composition according to claim 4, wherein the compound (A) having four or more isocyanate groups in one molecule has a molecular weight of 500 or more. 6. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiation system contains a titanocene compound. 7. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiation system contains a sensitizer that absorbs in a visible light region. 8. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiation system contains a sensitizer that absorbs in the near-infrared light region. 9. The photopolymerizable composition according to claim 1, further comprising a polymer binder. 10. A photosensitive lithographic printing plate having, on a support, a layer comprising the photopolymerizable composition according to any one of claims 1 to 9. 11. A laser scanning exposure apparatus.
The photosensitive lithographic printing plate described in 1. 12. The photopolymerizable composition according to claim 8, wherein the sensitizer is a cyanine dye. 13. The photopolymerizable composition according to claim 12, wherein the cyanine dye has a heterocyclic ring on a polymethine chain. 14. The photopolymerizable composition according to claim 12, wherein the photopolymerization initiation system contains an organic boron anion and / or a halomethyl group-containing compound. 15. The photopolymerizable composition according to claim 12, which contains an amine compound having at least an atomic group [N—CH ₂ ]. 16. The photosensitive layer further comprises a pK at 25 ° C.
An amine compound wherein b is 7 or less.
16. The photosensitive lithographic printing plate according to any one of 15. 17. A photosensitive lithographic printing plate comprising, on a support, a layer comprising the photopolymerizable composition according to claim 12, wherein the layer comprising the photopolymerizable composition is the uppermost layer. 18. After the photosensitive lithographic printing plate according to claim 10 or 11 is image-exposed by a laser beam to photo-cure the photosensitive layer in an image-wise manner, the layer comprising the photopolymerizable composition is not cured. A method for forming a photo-cured photosensitive image by removing an exposed portion from a support, characterized by removing the unexposed portion of the photosensitive layer from the support by developing with an alkali developing solution after image exposure. How to make a printing plate. 19. The photosensitive lithographic printing plate according to claim 17, which is image-exposed by a laser beam having a wavelength of 650 to 1300 nm to photo-cure the photosensitive layer in an image-wise manner, and then comprises a photopolymerizable composition. A method for forming a photocurable photosensitive image by removing an unexposed portion of a layer from a support, comprising developing the unexposed portion of the photosensitive layer from the support by developing with an alkali developing solution after image exposure. Characteristic printing plate making method.