JP2000347393A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the image recording material high in sensitivity to infrared laser beams and good in development latitude and storage stability. SOLUTION: The image recording material contains at least (a) a compound to be decomposed by light or heat and to generate an acid, (b) a cross-linking agent to be induced to cross-link by an acid, (c) a polymer compound insoluble in water and soluble in an aqueous alkali solution, and (d) an anionic infrared absorber represented by the formula: |Ga-M-Gb|mXm+ in which M is a conjugated chain; Ga is an anionic substituent; Gb is a neutral substituent; Xm+ is an H ion or an m-valent cation; and (m) is an integer of 1-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative type image recording material, and more particularly to a so-called direct plate making which can be written by heat of an infrared laser, a thermal head or the like and can be directly made from a digital signal of a computer or the like. The present invention relates to a negative type image recording material suitable for a lithographic printing plate material.

[0002]

2. Description of the Related Art In recent years, with the development of solid-state lasers and semiconductor lasers having an emission region from near infrared to infrared, as a system for directly making a plate from digital data of a computer,
Attention is paid to those using these infrared lasers.
As a negative-type image recording material recordable with an infrared laser, there is a recording material comprising an onium salt, a resole resin, a novolak resin, and an infrared absorber described in JP-A-7-20629. This is because in a lithographic printing plate using an image recording material, the energy given by a solid-state laser or semiconductor laser that emits infrared light is converted into thermal energy by an infrared absorber, and the onium salt is decomposed by the heat. Thus, an image is formed. That is, image recording, that is, plate-making of a recording material, is performed by promoting the crosslinking reaction between a binder and a crosslinking agent which is crosslinked by the acid, generated by the decomposition of the onium salt. However, the infrared absorber used in this case was a cationic dye alone, and there was a problem that a good image could not be obtained (low sensitivity, narrow development latitude) due to a small amount of heat generated by exposure. Here, the development latitude indicates an allowable range in which a good image can be formed when the alkali concentration of the alkali developer is changed. In addition, there is a problem that sensitivity fluctuation before and after storage in a high temperature and high humidity environment, that is, storage stability is poor.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention enables direct plate making by recording from digital data of a computer or the like using a solid-state laser and a semiconductor laser that emit infrared light, has high sensitivity to the infrared laser, and has development latitude and storage. An object of the present invention is to provide a negative-type image recording material having good stability.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies for the purpose of improving image forming properties (sensitivity and development latitude) and storage stability, and as a result, have found that an anionic infrared absorber is used. As a result, a high-sensitivity image can be formed, and the present invention has been completed. This is probably because the use of the anionic infrared absorber makes it possible to control the interaction of the counter cation with the binder. That is, in the case of a conventionally known cationic infrared absorber, its structure is naturally limited in order to have absorption in the infrared region, and the structure that interacts with the binder is limited to a range that does not hinder the absorption capacity in the infrared region. However, at present, the desired interaction cannot be controlled on the molecular structure. When an anionic infrared absorber is used as in the present invention, the counter cation can be freely selected, and the interaction with the binder can be freely changed without any restriction. It is considered that the formability could be improved. In addition, particularly, a compound that generates an acid by heat (hereinafter, referred to as “
It is referred to as "acid generator". In the case of ()), the distance between the anionic infrared absorber and the chaotic acid generator in the membrane is short due to ionic bonding, and the heat from the infrared absorber is efficiently transferred to the acid generator. It is thought that it is possible. The means for solving the above problems are as follows. That is, <1> an image recording material characterized by containing at least the following (a) to (d). (A) a compound that decomposes by light or heat to generate an acid (b) a crosslinking agent that crosslinks with an acid (c) a polymer compound that is insoluble in water and soluble in an aqueous alkaline solution (d) Anionic infrared absorbent represented by (I)

[0005]

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(In the general formula (I), M represents a conjugated chain;
_a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a hydrogen ion or an m-valent cation,
m represents an integer of 1 to 6. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the image recording material of the present invention will be described in detail. The image recording material of the present invention comprises at least (a) a compound capable of decomposing by light or heat to generate an acid (acid generator), and (b) a cross-linking agent capable of being cross-linked by an acid (hereinafter, simply referred to as “cross-linking agent”). ), (C) a polymer compound that is insoluble in water and soluble in an aqueous alkali solution (hereinafter referred to as “alkali-soluble polymer”), and (d) represented by the general formula (I). It contains an anionic infrared absorber and, if necessary, other components.

[(D) Anionic infrared absorbent represented by the general formula (I)] The image recording material of the present invention is characterized by using an anionic infrared absorbent represented by the following general formula (I). And

[0009]

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In the general formula (I), M represents a conjugated chain, which may have a substituent or a ring structure.
The conjugated chain M can be represented by the following formula.

[0011]

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In the formula, R _{n + 1} , R _{n + 2} and R _{n + 3} each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group. , Thio group, sulfonyl group, sulfinyl group,
Represents an oxy group or an amino group, which may have a substituent, and may be connected to each other to form a ring structure. n represents an integer of 1 to 8.

When R _{n + 1} , R _{n + 2} , and R _{n + 3} each represent an alkyl group, the alkyl group may be a straight-chain, branched or branched alkyl group having 1 to 20 carbon atoms. And a cyclic alkyl group. Specifically, a methyl group, an ethyl group,
Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s- Butyl group, t-butyl group, isopentyl group,
Examples include a neopentyl group, a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, those having 1 to 1 carbon atoms
A straight-chain, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

These alkyl groups may have a substituent, and examples of the substituent include monovalent nonmetallic atomic groups other than hydrogen. Preferred examples include a halogen atom (-F, -Br, -C1, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, an amino group, N-alkylamino group, N, N-
Dialkylamino group, N-arylamino group, N, N-
Diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyl An oxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, an acylthio group,
Acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-
Arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-
Alkylureido group, N-arylureido group, N'-
Alkyl-N-alkylureido group, N′-alkyl-
N-arylureido group, N ′, N′-dialkyl-N
-Alkylureido group, N ', N'-dialkyl-N-
Arylureido group,

N'-aryl-N-alkylureido groups, N'-aryl-N-arylureido groups, N ',
An N′-diaryl-N-alkylureido group, N ′,
An N′-diaryl-N-arylureido group, an N′-alkyl-N′-aryl-N-alkylureido group,
An N′-alkyl-N′-aryl-N-arylureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, and conjugate base group thereof (hereinafter, “carboxylate”
That. ), Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl Group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-
SO ₃ H) and its conjugate base group (hereinafter referred to as “sulfonato group”), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, An N-arylsulfinamoyl group, an N, N-diarylsulfinamoyl group, an N-alkyl-N-arylsulfinamoyl group, a sulfamoyl group, an N-alkylsulfamoyl group,

N, N-dialkylsulfamoyl group, N
-Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group (-SO
₂ NHSO ₂ R, R represents an alkyl group. ) And its conjugate base group, N-arylsulfonylsulfamoyl group (-
SO ₂ NHSO ₂ Ar and Ar represent an aryl group. ) And its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ R, R represents an alkyl group.) And a conjugated base group, N- aryl sulfonyl carbamoyl group (-CONHSO ₂ Ar, Ar is an aryl group And its conjugated base group and alkoxysilyl group (-S
i (OR) ₃ and R represent an alkyl group. ), An aryloxysilyl group (—Si (OAr) ₃ , Ar represents an aryl group), a hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, a phosphono group (—PO ₃ H ₂ ) and The conjugate base group (hereinafter, referred to as “phosphonato group”), a dialkylphosphono group (—PO ₃ R ₂ , R represents an alkyl group), a diarylphosphono group (—PO ₃ Ar ₂ , Ar represents an aryl group) the represented.), alkyl aryl phosphono group _{(-PO 3 (R) (Ar} ), R is an alkyl group, Ar. represents an aryl group) monoalkyl phosphono group (-PO ₃
H (R) and R represent an alkyl group. ) And its conjugated base group (hereinafter referred to as “alkylphosphonate group”),

A monoarylphosphono group (—PO ₃ H (A
r) and Ar represent an aryl group. ) And its conjugate base group (hereinafter referred to as “arylphosphonato group”), its phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatooxy group”), its dialkylphosphonooxy group ( —OPO ₃ (R) ₂ , R represents an alkyl group), a diarylphosphonooxy group (—OPO 3
₃ (Ar) ₂ and Ar represent an aryl group. ), An alkylarylphosphonooxy group (—OPO ₃ (R) (Ar),
R represents an alkyl group and Ar represents an aryl group. ), A monoalkylphosphonooxy group (—OPO ₃ H (R), R represents an alkyl group) and its conjugate base group (hereinafter, referred to as “alkylphosphonatooxy group”), a monoarylphosphonooxy group (—OPO ₃ H (Ar) Ar represents an aryl group) and its conjugate base group (hereinafter, referred to as “arylphosphonatooxy group”), cyano group, nitro group,
Examples include an aryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups represented by R _{n + 1} , R _{n + 2} , and R _{n + 3.} Specific examples of the aryl group include , Phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, Phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group,
Methylaminophenyl group, dimethylaminophenyl group,
Acetylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, phenoxycarbonylphenyl, N-phenylcarbamoylphenyl, nitrophenyl, cyanophenyl, sulfophenyl, sulfonatophenyl, phosphono Examples include a phenyl group and a phosphonatophenyl group. Specific examples of the alkenyl group in the above substituent include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group, a 2-chloro-1-ethenyl group, and the like. Specific examples of the alkynyl group include Examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and a phenylethynyl group. In addition, the acyl group (R ¹ CO
As-), R ¹ represents a hydrogen atom, the above-mentioned alkyl group,
Those which are an aryl group, an alkenyl group, or an alkynyl group are mentioned.

Among these substituents, more preferred are a halogen atom (-F, -Br, -C1, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, , N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N- Alkylcarbamoyl group, N, N-
Dialkylcarbamoyl, N-arylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulfo, sulfonato, sulfamoyl, N-alkylsulfamoyl, N, N-dialkylsulfamoyl, N-aryl Sulfamoyl group, N-alkyl-N
-Arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonate group, monoarylphosphono group, arylphosphonate group, phosphonooxy group, phosphonatoxy group , An aryl group, an alkenyl group and the like.

On the other hand, examples of the alkylene group in the substituted alkyl group include those obtained by removing any one of the aforementioned hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. Preferably, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms are exemplified. Preferred specific examples of the substituted alkyl group obtained by combining the substituent and an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group,

A carboxypropyl group, a methoxycarbonylethyl group, a methoxycarbonylmethyl group, a methoxycarbonylbutyl group, an allyloxycarbonylbutyl group,
Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylgarbamoylmethyl group, N- (methoxyphenyl) galbamoylethyl group, N-methyl-N- (sulfophenyl) galva Moylmethyl group, sulfopropyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphospho Nopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl Group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl Group, 2-butynyl group, 3-butynyl group and the like. .

When R _{n + 1} , R _{n + 2} and R _{n + 3} represent an aryl group, the aryl group may be a group in which 1 to 3 benzene rings form a condensed ring, a benzene ring And a 5-membered unsaturated ring to form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Among them, a phenyl group and a naphthyl group are more preferred.

When R _{n + 1} , R _{n + 2} , and R _{n + 3} represent a substituted aryl group, the substituted aryl group may be a hydrogen atom on the ring-forming carbon atom of the aryl group. And those having a monovalent nonmetallic atomic group other than. Preferred examples of the substituent include the alkyl group, the substituted alkyl group, and the substituents described above for the substituted alkyl group. Preferred specific examples of such a substituted aryl group include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, phenylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyl Oxyphenyl group, benzoyloxyphenyl group, N
-Cyclohexylcarbamoyloxyphenyl group, N-
Phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group,

Methoxycarbonylphenyl, allyloxycarbonylphenyl, chlorophenoxycarbonylphenyl, galbamoylphenyl, N-methylgalbamoylphenyl, N, N-dipropylcarbamoylphenyl, N- (methoxyphenyl) galva Moylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoyl Phenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group , L-phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl Group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like.

R _{n + 1} , R _{n + 2} and R _{n + 3} each represent an alkenyl group, a substituted alkenyl group, an alkynyl group,
Or a substituted alkynyl group (—C (R ² ) = C (R ³ )
(R ⁴ ), —C≡C (R ⁵ )), R ² ,
R ³ , R ⁴ and R ⁵ each represent a monovalent nonmetallic atomic group. Preferred examples of R ² , R ³ , R ⁴ , and R ⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group.
Specific examples of these are the same as those described above. Particularly preferred examples of R ² , R ³ , R ⁴ , and R ⁵ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

Specific examples of the above R ² , R ³ , R ⁴ and R ⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. Group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, otatadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t
-Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenyl group, 2
-Propynyl group, 2-butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylhensyl group, 1-
Methyl-1-phenethyl group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group,
Phenoxydiethyl, allyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl,

Morpholinoethyl group, morpholinopropyl group, sulfopropyl group, sulfonatopropyl group, sulfobutyl group, sulfonatobutyl group, carboxydimethyl group,
Carboxydiethyl, carboxypropyl, methoxycarbonylethyl, 2-ethylhexyloxycarbonylethyl, phenoxycarbonylmethyl, methoxycarbonylpropyl, N-methylcarbamoylethyl, N, N-ethylaminocarbamoylmethyl, N
-Phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, P-trienesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, phosphonoethyl group, phosphonopropyl group, p
-Phosphonobenzylaminocarbonylethyl group, phosphonatomethyl group, phosphonatopropyl group, phosphonatobutyl group, p-phosphonatobenzylaminocarbonylethyl group, vinyl group and ethynyl group.

When R _{n + 1} , R _{n + 2} and R _{n + 3} represent a substituted carbonyl group (R ⁶ CO—), R ⁶ represents a monovalent nonmetallic atomic group. Preferred examples of the substituted carbonyl group include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-
Examples include a dialkylcarbamoyl group, an N-arylcarbamoyl group, an N, N-diarylcarbamoyl group, and an N-alkyl-N-arylcarbamoyl group. Examples of the alkyl group and the aryl group in these include those exemplified above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Among these,
More preferred substituted carbonyl groups include a formyl group,
Acyl group, carboxyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, galbamoyl group, N-alkylgalbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, and particularly preferred are formyl group, acyl group, alkoxycarbonyl group, and aryl group. And a roxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group And a morpholinocarbonyl group.

The above R_{n + 1}, R_{n + 2}, And R_{n + 3}Is replaced
O group (R⁷When S-) is represented, R ⁷Is one except hydrogen
Represents a valent non-metallic atomic group. Examples of preferred substituted thio groups
Alkylthio, arylthio, alkyldithio
Groups, aryldithio groups, and acylthio groups.
You. As the alkyl group and the aryl group in these,
The above alkyl group, substituted alkyl group, aryl group, and
Examples of the substituted aryl group include those exemplified as acyl.
An acyl group (R¹R of CO-)¹Is as above
It is a cage. Of these, alkylthio groups and ants
A thio group is more preferred. Preferred specific examples of the substituted thio group
Examples include methylthio, ethylthio, phenylthio
O group, ethoxyethylthio group, carboxyethylthio
Group, methoxycarbonylthio group and the like.

When R _{n + 1} , R _{n + 2} and R _{n + 3} represent a substituted sulfonyl group (R ⁸ SO ₂ —), R ⁸ represents a monovalent nonmetallic atomic group. More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group, substituted alkyl group, aryl group,
And substituted aryl groups.
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

When R _{n + 1} , R _{n + 2} and R _{n + 3} represent a substituted sulfinyl group (R ⁹ SO—), R ⁹ represents a monovalent nonmetallic atomic group. Preferred examples include alkylsulfinyl, arylsulfinyl, sulfinamoyl, N-alkylsulfinamoyl, N, N
-Dialkylsulfinamoyl, N-arylsulfinamoyl, N, N-diarylsulfinamoyl and N-alkyl-N-arylsulfinamoyl. Examples of the alkyl group and the aryl group in these include those exemplified above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Among these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

When R _{n + 1} , R _{n + 2} and R _{n + 3} represent a substituted oxy group (R ¹⁰ O—), R ¹⁰ is a monovalent nonmetallic atomic group except hydrogen. Represent. Preferred substituted oxy groups include alkoxy, aryloxy, acyloxy, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N, N
-Dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, and phosphonatoxy group. Examples of the alkyl group and the aryl group in these include those exemplified above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group.

Examples of the acyl group (R ¹ CO—) in the acyloxy group include those in which R ¹ has been exemplified as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Among these substituted oxy groups, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferred. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy,
Dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group,
Methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group , Xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromophenyloxy, acetyloxy, benzoyloxy, naphthyloxy, phenylsulfonyloxy, phosphonooxy, phosphonatoxy And the like.

[0034] The _{R n + 1, R n +} 2, and R _{n + 3,} a substituted amino group - If ^{(R 11 NH, (R 12} ) (R 1 3) N-) representative of said R ^11, R ¹² and R ¹³ each represent a monovalent nonmetallic atomic group other than hydrogen. Preferred examples of the substituted amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group ,
N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-
Arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N- Arylureido group,
An N ′, N′-diaryl-N-alkylureido group,
An N ′, N′-diaryl-N-arylureido group,
N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy A carbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group.

Examples of the alkyl group and the aryl group in these compounds include those exemplified as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group, and include an acylamino group, an N-alkylacylamino group,
An acyl group (R ¹ C) in the aryl-acylamino group;
R ^{1 in} O-) is as described above. Of these, more preferred are N-alkylamino group, N,
Examples include an N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include a methylamino group, an ethylamino group, a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, and an acetylamino group.

[0036] In the general formula (I), G _a ^- represents an anionic substituent, may have a ring structure. G _b represents a neutral substituent and may have a ring structure. These can be represented by the following structures, respectively.

[0037]

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Where L₁~ L_FourAre independent of each other
Atom, halogen atom, cyano group, the aforementioned alkyl group,
Alkenyl group, alkynyl group, carbonyl group,
Thio group, sulfonyl group, sulfinyl group, oxy group, or
Represents an amino group, and L ₁And L_Two, L_ThreeAnd L_FourAre linked
To form a ring structure. As a preferred example, G_bIs
Acidic nuclei of cyanine dyes;_a ^-Is an acid nucleus
Turned on. As the acidic nucleus, "The
 teory of the Photographi
c Process "p, 199, Table 8, 2-B
And the following compounds.

1) 1,3-dicarbonyl nucleus, for example,
1,3-indandione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione, 2) pyrazolinone nucleus, for example, 3-methyl- 1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-
5-one, 1- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one, 3) isoxazolinone nucleus, for example, 3-phenyl-2
-Isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc. 4) Oxindole nucleus, for example, 1-alkyl-2,
3-dihydro-2-oxindole,

5) 2,4,6-triketohexahydropyrimidine nucleus, for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof, such derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-diethyl and 1,3-dibutyl,
3-diphenyl, 1,3-di (p-chlorophenyl)
And 1,3-diaryl compounds such as 1,3-di (p-ethoxycarbonylphenyl) and 1-alkyl-3-aryl compounds such as 1-ethyl-3-phenyl. 6) 2-thio-2,4-thiazolidinedione nucleus, for example, rhodanine and derivatives thereof, such as 3-ethylrhodanine, 3-allylrhodanine and other 3-alkylrhodanine, 3-phenylrhodanine And the like.

7) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione) nucleus, for example, 2-ethyl-2-thio-2,4
8) thianaphthenone nucleus, such as 3 (2H) -thianaphthenone and 3 (2H) -thianaphthenone-1,1-dioxide; 9) 2-thio-2,5-thiazolidinedione nucleus, such as 3- Ethyl-2-thio-2,5-thiazolidinedione, 10) 2,4-thiazolidinedione nucleus, for example, 2,4
-Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, 11) thiazolidinone nucleus, for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone,

12) 4-thiazolinone nucleus, for example, 2-
Ethyl mercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, 13) 2-imino-2-oxozolin-4-one (coagulation hydantoin) nucleus, 14) 2,4- Imidazolidinedione (hydantoin)
A nucleus, for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 15) 2-thio-2,4-imidazolidinedione (2-
Thiohydantoin) nucleus, for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-
16) 2-imidazolin-5-one nucleus, for example 2-n
-Propyl-mercapto-2-imidazolin-5-one,

17) Furan-5-one, 18) 4-hydroxy-2 (1H) -quinolinone nucleus or 4-hydroxy-2 (1H) -pyridinone nucleus, for example, N-methyl-4-hydroxy-2 (1H) ) -Quinolinone, Nn-butyl-4-hydroxy-2 (1H)-
Quinolinone, N-methyl-4-hydroxy-2 (1H)
-Pyridinone, 19) substituted or unsubstituted 4-hydroxy-2H-pyran-2-one, 4-hydroxycoumarin, 20) substituted or unsubstituted thioindoxyl, for example, 5-methylthioindoxyl.

In the above formula, Z is a chalcogen atom,
Or -C (Y ₁₎ representative of the (Y ₂₎ group. Where Y ₁ and Y
₂ may be the same or different and each is -CN,
Represents —CO ₂ R ′ or —SO ₂ R ″. R 'and R''
Represents the same alkyl group or aryl group as described above.

In the general formula (I), X ^{m +} (hereinafter sometimes referred to as “counter cation”) represents a hydrogen ion or an m-valent cation. Here, m represents an integer of 1 to 6.
Preferred embodiments of the anionic infrared absorber,
The counter cation interacts with the binder,
Examples of such a counter cation include those having an onium salt structure. Here, examples of the onium salt include ammonium salts, diazonium salts, oxonium salts, sulfonium salts, selenium salts, phosphonium salts, carbonium salts, iodonium salts and the like.

Suitable onium salts include, for example, S. I. Schlesinger, Photog
r. Sci. Eng. , 18, 387 (1974),
T. S. Bal et al, Polymer, 21,
423 (1980), JP-A-5-158230, diazonium salts described in U.S. Pat. No. 4,069,055.
No. 4,069,056, JP-A-3-140140
Ammonium salts described in JP-A No. C. Necker
et al, Macromolecules, 17,
2468 (1984), C.I. S. Wen et al,
Teh, Proc. Conf. Rad. Curing
ASIA, p478 Tokyo, Oct (198
8) U.S. Pat. Nos. 4,069,055 and 4,06
9,056, the phosphonium salt described in J. V. Cri
vello et al, Macromorecule
s, 10 (6), 1307 (1977), Chem. &
Eng. News, Nov .; 28, p31 (198
8), EP 104,143, US Patent 33
No. 9,049, No. 410,201, JP-A-2-15
No. 0848 and JP-A-2-296514. V. Crivello et al, P
polymer J .; 17, 73 (1985); V.
Crivello et al. J. Org. Che
m. 43, 3055 (1978); R. Watt
et al, J.A. Polymer Sci. , Pol
ymer Chem. Ed. , 22, 1789 (198
4). V. Crivello et al, Pol
ymer Bull. , 14, 279 (1985),
J. V. Crivello et al, Macrom
orecules, 14 (5), 1141 (198
1). V. Crivello et al, J. Mol. P
polymer Sci. , Polymer Chem.
Ed. , 17, 2877 (1979), EP 37
No. 0,693, No. 233,567, No. 297,443
No. 297,442, U.S. Pat. No. 4,933,37.
7, 3,902,114, 410,201,
No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580
No. 3,604,581, the sulfonium salt described in
J. V. Crivello et al, Macrom
orecules, 10 (6), 1307 (197
7). V. Crivello et al, J. Mol. P
polymer Sci. , Polymer Chem.
Ed. , 17, 1047 (1979); S. Wen et al, Teh, Pro
c. Conf. Rad. Curing ASIA, p4
78 Tokyo, Oct (1988).

Further, ammonium salts, phosphonium salts, sulfonium salts, iodonium salts and the like described in JP-A-9-134909 can be preferably used in the present invention.

The oxonium salt has the following general formula (A)
Or, it is represented by the general formula (B).

[0049]

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In the formula, R _{a to} R _d each independently represent an alkyl group or an aryl group, R _e represents an alkylene group,
Or an arylene group. Adjacent R _{a to} R _c or R _d and R _e may be bonded to each other to form a ring structure.

The selenium salt is represented by the following general formula (C) or (D).

[0052]

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In the formula, R _{f to} R _i each independently represent an alkyl group or an aryl group, R _j represents an alkylene group,
Or an arylene group. Further, adjacent R _{f to} R _g , or R _i and R _j may be bonded to each other to form a ring structure.

The diazonium salt has the following general formula (E)
It is represented by

[0055]

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In the formula, R _k represents an alkyl group or an aryl group.

The carbonium salt is represented by the following general formula (F)
Or it is represented by general formula (G).

[0058]

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[0059] In the formula, R _l to R _o are each independently an alkyl group or an aryl group, R _p is an alkylene group,
Or an arylene group. Adjacent R _{1 to} R _m , or R _o and R _p may be bonded to each other to form a ring structure.

Other preferred onium salts include those represented by the following general formulas (H) to (K).

[0061]

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In the above formula, R ^A , R ^B , R ^C , R ^D , R ^J ,
R ^K , R ^L, and R ^M each independently represent an alkyl group, an aryl group, or an aralkyl group; R ^A , R ^B , R ^C, and R ^D may be bonded to each other to form a ring; R ^J ,
R ^K , R ^L and R ^M may combine with each other to form a ring. R ^E , R ^F and R ^G are each independently an alkyl group,
Or an aryl group, and R ^E , R ^F and R ^G may be bonded to each other to form a ring. R ^H and R ^I each independently represent an alkyl group.

A more preferred example is an embodiment in which the counter cation is a thermally decomposable onium salt. The term "thermally decomposable onium salt" means an onium salt having a temperature at which decomposition occurs at 10 mol% and a temperature of 200 ° C. or lower as measured by a differential thermal / thermogravimetric analysis or a melting point measuring device. Such a thermally decomposable onium salt can be easily obtained by changing the substituent of the onium salt. As the thermally decomposable onium salt used here, as long as it satisfies the above requirements for thermal decomposability, ammonium salts, diazonium salts, oxonium salts, sulfonium salts, selenium salts, phosphonium salts, carbonium salts, iodonium salts, etc. Any of them may be used.

In the general formula (I), the anionic dye skeleton can be represented by the following general formula (II).

[0065]

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Here, θ, α, and φ are variables, and a specific structure of the anionic dye skeleton can be represented by a combination of the respective partial structures G _a θ, Mα φ, and G _b θ. For example, the partial structures G _a1 , M _f3 , G
_{When b2} is as _follows ,

[0067]

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The anionic dye skeleton obtained by combining these has the following structure.

[0069]

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Hereinafter, examples of the partial structure of the anionic dye skeleton, examples of the anionic dye skeleton, and specific examples of onium salts that are preferable as counter cations are shown. However, the present invention is not limited to these specific examples. Absent. Examples of the partial structure G _a θ include the following.

[0071]

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[0072]

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The following are examples of the partial structure G _b θ.

[0074]

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[0075]

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Examples of the methine chain Mαφ include the following.

[0077]

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[0078]

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Examples of the substituent Y when the methine chain Mαφ has a substituent include the following.

[0080]

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[0081]

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The following are examples of the anionic dye skeleton.

[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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Examples of suitable counter cation partial structures represented by the general formulas (A) to (G) include the following.

[0099]

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Examples of suitable counter cation partial structures represented by formula (H) include the following.

[0101]

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Examples of suitable counter cation partial structures represented by the above general formula (I) include the following.

[0103]

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[0104]

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Examples of suitable counter cation partial structures represented by the general formula (J) include the following.

[0106]

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Examples of suitable counter cation partial structures represented by the general formula (K) include the following.

[0108]

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[0109]

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The synthesis of the anionic infrared absorbent used in the present invention can be carried out by condensing a compound having active methylene with a methylene chain donor in the presence of a base. This synthesis method is a general synthesis method of a dye,
For example, "Dyes and Chemicals" (1991) 274-28
It can be carried out according to the method for synthesizing oxonol dyes described on page 9.

In the present invention, oxonol-based dyes represented by the above general formula (I) are preferred in terms of absorbance and the like. Examples of such dyes include EP 444,786 and EP 3
No. 97,435, and preferably Japanese Patent Application No.
-79912, Japanese Patent Application No. 10-237634, and Japanese Patent Application No. 10-270097.
Further, those described in JP-A-10-297103 can also be used.

In the present invention, these anionic infrared absorbents are used in an amount of 0.04% to the total solid content of the image recording material.
It can be added at a rate of 1 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight. If the amount is less than 0.01% by weight, an image cannot be formed with this image recording material, and
When added in excess of 0% by weight, when used as a photosensitive layer of a lithographic printing plate precursor, stains may occur on non-image areas.

To the image recording material of the present invention, other pigments or dyes having an infrared absorbing property can be added in addition to the infrared absorbing agent as long as the effects of the present invention are not impaired. Examples of the pigment include commercially available pigment and color index (CI) handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology"
(CMC Publishing, 1986), "Printing ink technology" C
MC Publishing, 1984) can be used.

Examples of the 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 pigments. . 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.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic 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 0.01 to 10 μm, more preferably 0.05 to 1 μm, and 0.1 to 10 μm.
1 μm is particularly preferred. The particle size of the pigment is 0.01 μm
When it is less than 10 μm, it is not preferable in terms of stability of the dispersion in the coating solution of the photosensitive layer, and when it exceeds 10 μm, it is not preferable in terms of uniformity of the photosensitive layer. 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. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

Examples of the dye include commercially available dyes and literatures (eg, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, Showa 45)
Known publications described in the annual publication can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment absorbing infrared light or near infrared light, carbon black is preferably used. Further, examples of dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829,
Cyanine dyes described in JP-A-60-78787, JP-A-58-173696, JP-A-58-18
1690, methine dyes described in JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187,
JP-A-59-73996, JP-A-60-52940
Naphthoquinone dyes described in JP-A-60-63744, squarylium dyes described in JP-A-58-112792, etc., British Patent 434,875
And the dihydroperimidine squarylium dye described in U.S. Pat. No. 5,380,635.

Further, US Pat.
The near-infrared absorption sensitizer described in US Pat. No. 6,938,938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 7-142645 (U.S. Pat. No. 4,327,169)
No. 3) described in JP-A-58-1983.
No. 181051, No. 58-220143, No. 59-4
Nos. 1363, 59-84248, 59-8424
No. 9, No. 59-146063, No. 59-146061
Pyrylium compounds described in JP-A-59-
No. 216146, US Pat.
Pentamethine thiopyrylium salt described in JP-A-83,475, pyrylium compounds disclosed in JP-B-5-13514 and JP-A-5-19702, and Epollight.
III-178, Epollight III-130, Ep
light III-125, Epolight IV-
62A and the like are particularly preferably used. Another particularly preferred example of the dye is disclosed in U.S. Pat.
No. 6,993, near-infrared absorbing dyes described as formulas (I) and (II).

These dyes or pigments may be added to the image-recording material of the present invention and added to the photosensitive layer together with other components. A layer may be provided and added thereto. These dyes or pigments may be used alone or in combination of two or more.

[(A) Acid Generator] In the present invention, the compound capable of decomposing by light or heat to generate an acid is 200 to 5
It means a compound that generates an acid upon irradiation with light having a wavelength of 00 nm or heating at 100 ° C. or higher. As the acid generator suitably used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known acid generators and the like, known compounds that generate an acid upon thermal decomposition, and mixtures thereof, and the like, and cationic acid generators are particularly preferred. The reason is that since the infrared absorber used in the present invention is anionic, the distance between the anionic infrared absorber and the cationic acid generator in the membrane is short due to ionic bonding, and the infrared absorber is efficiently separated from the infrared absorber. It is considered that this heat can be transferred to the acid generator.

For example, S.I. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974); S. Bal et al, Poly
mer, 21,423 (1980), U.S. Pat. Nos. 4,069,055 and 4,062.
9,056 and Re27,992, and ammonium salts described in JP-A-4-365049;
D. C. Necker etal, Macromole
cules, 17, 2468 (1984), C.I. S. W
en et al, Teh, Proc. Conf. Ra
d, CuringASIA, p478 Tokyo, O
ct (1988), U.S. Pat. No. 4,069,055,
The phosphonium salts described in each specification of JP-A-4,069,056; V. Crivello et al, Mac
romolecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov .; 2
8, p31 (1988), EP 104,143.
Nos. 339,049 and 410,201.
No., JP-A-2-150848, JP-A-2-150848
Iodonium salts described in each publication of J.
V. Crivello et al, Polymer
J. 17, 73 (1985); V. Crivell
o et al. J. Org. Chem. , 43,30
55 (1978); R. Watt et al,
J. Polymer Sci. , Polymer Ch
em. Ed. , 22, 1789 (1984); V.
Crivello et al, Polymer

Bull. , 14, 279 (1985),
J. V. Crivello et al, Macrom
olecules, 14 (5), 1141 (198
1). V. Crivello et al, J. Mol. P
polymer Sci. , Polymer Chem.
Ed. , 17, 2877 (1979), EP 37
Nos. 0,693, 390,214, 233,567
Nos. 297,443 and 297,442; U.S. Pat. Nos. 4,933,377; 161,811;
No. 10,201, No. 339,049, No. 4,760,
No. 013, No. 4,734,444, No. 2,833,8
No. 27, German Patent Nos. 2,904,626 and 3,60
4,580, 3,604,581, the sulfonium salt described in each specification,

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977); V. Crivello et a
1, J .; Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979); S. Wen et al, Te
h, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), US Pat.
No. 05,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-55-32070.
0-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, and JP-A-63-298339. Organic halogen compounds, K. Meier et al, J. Mol. Rad. Cur
ing, 13 (4), 26 (1986); P. Gi
ll et al, Inorg. Chem. , 19,3
007 (1980); Astruc, Acc. Ch
em. Res. , 19 (12), 377 (1896),
Organometallic / organic halides described in JP-A-2-161445; Hayase et al, J. Mol. P
polymer Sci. , 25, 753 (1987),
E. FIG. Reichmanis et al. Poly
mer Sci. , Polymer Chem. E
d. , 23, 1 (1985); Q. Zhu et
al, J Photochem. , 36, 85, 39,
317 (1987); Amit et al, Te
trahedron Lett. , (24) 2205
(1973),

D. H. R. Barton et al,
J. Chem. Soc. 3571 (1965);
M. Collins et al, J. Mol. Chem. So
c. , Perkin I, 1695 (1975);
Rudinstein et al, Tetrahed
ron Lett. , (17), 1445 (197
5). W. Walker et al, J.A. Am.
Chem. Soc. , 110, 7170 (1988),
S. C. Busman et al, J. M .; Imagin
gTechnol. , 11 (4), 191 (198
5), H. M. Houlihan et al, Mac
romolecules, 21, 2001 (198
8), p. M. Collins et al, J. Mol. Ch
em. Soc. Chem. Commun. , 532
(1972); Hayase et al, Mac
romolecules, 18, 1799 (198
5), E. Reichmanis et al. E
electrochem. Soc. , SolidStat
e Sci. Technol. , 130 (6);
M. Houlihan et al, Macromol
ecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083 and 15
6,535, 271 and 851, 0,388,3
No. 43, U.S. Pat. Nos. 3,901,710 and 4,18
1,531, JP-A-60-198538
Described in each gazette of JP-A-53-133022.
A photoacid generator having a nitrobenzyl-type protecting group; Tu
nooka et al, Polymer Prepr
ints Japan, 38 (8); Berner
et al, J.A. Rad. Curing, 13
(4); J. Mijs et al, Coatin
gTechnol. , 55 (697), 45 (198
3), Akzo, H .; Adachi et al, Po
lymer Preprints, Japan, 37
(3), European Patent Nos. 0199,672 and 84515
Nos. 199,672, 044,115, 01
No. 01,122, U.S. Pat. Nos. 4,618,564, 4,371,605 and 4,431,774, JP-A-64-18143, JP-A-2-2457.
No. 56, compounds disclosed in Japanese Patent Application Nos. 3-140109 and the like, compounds which generate sulfonic acid by photolysis, such as iminosulfonates, and disulfone compounds described in JP-A-61-166544. Is mentioned.

Compounds in which these acid-generating groups or compounds are introduced into the main chain or side chain of the polymer, for example, M.P. E. FIG. Woodhouse et al, J. Mol.
Am. Chem. Soc. , 104, 5586 (198
2), S.M. P. Pappaset al, J .; Imag
ing Sci. , 30 (5), 218 (1986),
S. Kondo et al. Makromol. Ch
em. , RapidCommun. , 9, 625 (19
88), Y. Yamada et al, Makrom
ol. Chem. , 152, 153, 163 (197
2). V. Crivello et al. J. P
polymer Sci. , Polymer Chem.
Ed. , 17, 3845 (1979); U.S. Pat.
849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-1.
No. 64824, JP-A-62-69263, JP-A-63-69263
Compounds described in JP-A-146037, JP-A-63-163452, JP-A-62-153853, and JP-A-63-146029 can be used.

Further, V.I. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. ,
(47) 4555 (1971); H. R. Bart
on et al, J.A. Chem, Soc,. (C),
329 (1970); U.S. Pat. No. 3,779,778.
And compounds capable of generating an acid by light described in the specifications of European Patent No. 126,712 and the like can also be used.
Among these, examples of the acid generator particularly preferably used in the present invention include compounds represented by the following general formulas (I) to (V).

[0128]

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In the general formulas (I) to (V), R¹, R^Two,
R^FourAnd R^FiveMay be the same or different, and the substituent
The hydrocarbon groups having 20 or less carbon atoms that may be
You. R ^ThreeMay have a halogen atom or a substituent
Hydrocarbon group having 10 or less carbon atoms or 10 or less carbon atoms
Represents an alkoxy group. Ar¹, Ar^TwoAre the same but different
Having 20 carbon atoms which may have a substituent
Represents up to two aryl groups. R⁶Has a substituent
Represents a divalent hydrocarbon group having 20 or less carbon atoms.
n represents the integer of 0-4.

In the above general formulas (I) to (V),
R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent,
It preferably represents a hydrocarbon group having 1 to 14 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, and n-
Propyl group, i-propyl group, n-butyl group, sec-
Butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, undecyl group, alkyl group such as dodecyl group, allyl group, vinyl group,
Alkenyl groups such as 1-methylvinyl group and 2-phenylvinyl group, aralkyl groups such as benzyl group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, anthracenyl And an aryl group such as a group. These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a chloroethyl group, a 2-methoxyethyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a methoxyphenyl group, a phenoxyphenyl group, Examples include a methoxyphenylvinyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, and a 9,10-dimethoxyanthracenyl group.

In the general formulas (I) to (V), R ³
Is a halogen atom, an optionally substituted 1 carbon atom
It represents a hydrocarbon group having 0 or less (for example, an alkyl group, an alkenyl group, an aralkyl group, or an aryl group) or an alkoxy group having 10 or less carbon atoms. Specifically, fluorine, chlorine,
Halogen atom such as bromine and iodine, methyl group, ethyl group,
n-propyl group, i-propyl group, allyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group,
Hydrocarbon groups such as cyclohexyl group, benzyl group, phenyl group and tolyl group, and hydrocarbon groups having substituents such as 2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group and methoxyphenyl group And methoxy and ethoxy groups. When n is 2 or more, two adjacent R ³ may be bonded to each other to form a condensed ring.

In the general formulas (I) to (V), Ar
¹ and Ar ² may be the same or different and represent an optionally substituted aryl group having 20 or less carbon atoms, preferably an aryl group having 6 to 14 carbon atoms. Specifically, phenyl, tolyl, xylyl, cumenyl, mesityl, dodecylphenyl, phenylphenyl, naphthyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, chloronaphthyl, Methoxyphenyl group, phenoxyphenyl group, ethoxynaphthyl group, nitrophenyl group, cyanophenyl group, carboxyphenyl group, nitronaphthyl group,
And an anthracenyl group.

In the general formulas (I) to (V), R ⁶
Represents a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent (for example, an alkylene group, an alkenylene group, an aralkylene group, and an arylene group). Specifically, an ethynylene group, a 1,2-cyclohexenylene group,
1,2-phenylene group, 4-chloro-1,2-phenylene group, 4-nitro-1,2-phenylene group, 4-methyl-1,2-phenylene group, 4-methoxy-1,2-phenylene group A 4-carboxy-1,2-phenylene group,
Examples include a 1,8-naphthalenylene group. n is 0 to 4
Represents an integer. Here, when n is 0, it means that there is no R ³ , that is, it is a hydrogen atom.

Preferred compounds among the compounds represented by formulas (I) to (V) are described below. These compounds can be synthesized, for example, by the methods described in JP-A Nos. 2-100054 and 2-100055.

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[0136]

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[0138]

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[0139]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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(A) As an acid generator, an onium salt having a counter ion of a halide or sulfonic acid, preferably an iodonium salt, a sulfonium salt or a diazonium salt represented by the following general formulas (VI) to (VIII): Those having any of the structural formulas are also preferably mentioned.

[0147]

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In the above general formulas (VI) to (VIII), X
^- is a halide _{^{ion, ClO 4 -, PF 6 -}} , SbF 6
^-, BF ₄ ^-, or R ⁷ -SO ₃ ^- and the like, wherein, R ⁷
Represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ and Ar ⁴ each represent an aryl group having 20 or less carbon atoms which may have a substituent. R
⁸ , R ⁹ and R ¹⁰ each represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent.

In the general formulas (VI) to (VIII), R ⁷ —SO ₃ ^— is particularly preferably used as X ⁻ , wherein R ⁷ is a carbon atom which may have a substituent. Represents a hydrocarbon group having a number of 20 or less. Specific examples of the hydrocarbon group represented by R ⁷ include a methyl group, an ethyl group, and n-
Propyl, i-propyl, allyl, n-butyl, sec-butyl, t-butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl,
Alkyl groups such as dodecyl group, alkenyl groups such as vinyl group, 1-methylvinyl group and 2-phenylvinyl group, aralkyl groups such as benzyl group and phenethyl group, phenyl group, tolyl group, xylyl group, cumenyl group and mesityl group And aryl groups such as dodecylphenyl group, phenylphenyl group, naphthyl group and anthracenyl group. These hydrocarbon groups have, for example, substituents such as a halogen atom, a hydroxy group, an alkoxy group, an allyloxy group, a nitro group, a cyano group, a carbonyl group, a carboxyl group, an alkoxycarbonyl group, an anilino group, and an acetamido group. You may. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-methoxyethyl group,
0-campanyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, methoxyphenyl, hydroxyphenyl, phenoxyphenyl, nitrophenyl, cyanophenyl, carboxyphenyl, methoxynaphthyl, dimethoxy Examples include an anthracenyl group, a diethoxyanthracenyl group, and an anthraquinonyl group.

In the above general formulas (VI) to (VIII), Ar ³ and Ar ⁴ each represent an aryl group having 20 or less carbon atoms which may have a substituent, and specifically, a phenyl group , Tolyl group, xylyl group, cumenyl group,
Mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, anthracenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, hydroxyphenyl group,
Phenoxyphenyl group, nitrophenyl group, cyanophenyl group, carboxyphenyl group, anilinophenyl group,
Examples include anilinocarbonylphenyl group, morpholinophenyl group, phenylazophenyl group, methoxynaphthyl group, hydroxynaphthyl group, nitronaphthyl group, anthraquinonyl group and the like.

In the general formulas (VI) to (VIII), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent,
Specifically, a methyl group, an ethyl group, an n-propyl group, i
-Propyl group, allyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group, cyclohexyl group,
Benzyl group, phenyl group, tolyl group, t-butylphenyl group, naphthyl group, hydrocarbon group such as anthracenyl group,
2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, hydroxyphenyl group, phenylthiophenyl group, hydroxynaphthyl group, methoxynaphthyl group, benzoylmethyl group, naphthoylmethyl group And the like. Further, R ⁸ and R ⁹ may be bonded to each other to form a ring.

Examples of the cation part of the onium salt represented by the general formulas (VI) to (VIII) include an iodonium ion, a sulfonium ion and a diazonium ion. Specific structures of the cation portion of these onium salts are shown below, but the invention is not limited thereto.

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[0154]

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[0156]

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[0157]

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On the other hand, among the counter anions of these onium salts, particularly preferred examples of the sulfonate ion include: 1) methanesulfonate, 2) ethanesulfonate, 3) 1-propanesulfonate, 4) 2-propanesulfonate. 5) n-butanesulfonate, 6) allylsulfonate, 7) 10-camphorsulfonate, 8) trifluoromethanesulfonate, 9) pentafluoroethanesulfonate, 10) benzenesulfonate, 11) p-toluenesulfonate, 12) 3-methoxy Benzenesulfonate, 13) 4-methoxybenzenesulfonate, 14) 4-hydroxybenzenesulfonate, 15) 4-chlorobenzenesulfonate, 16) 3-nitrobenzenesulfonate, 17) 4-d Lobenzenesulfonate, 18) 4-acetylbenzenesulfonate, 19) pentafluorobenzenesulfonate, 20) 4-dodecylbenzenesulfonate, 21) mesitylenesulfonate, 22) 2,4,6-triisopropylbenzenesulfonate, 23) 2-hydroxy -4-methoxybenzophenone-
5-sulfonate, 24) dimethyl-5-sulfonate isophthalate, 25) diphenylamine-4-sulfonate, 26) 1-naphthalene sulfonate, 27) 2-naphthalene sulfonate, 28) 2-naphthol-6-sulfonate, 29) 2- Naphthol-7-sulfonate, 30) anthraquinone-1-sulfonate, 31) anthraquinone-2-sulfonate, 32) 9,10-dimethoxyanthracene-2-sulfonate, 33) 9,10-diethoxyanthracene-2-sulfonate, 34 ) Quinoline-8-sulfonate, 35) 8-hydroxyquinoline-5-sulfonate, 36) 8-anilino-naphthalene-1-sulfonate and the like.

Also, 41) m-benzenedisulfonate, 42) benzaldehyde-2,4-disulfonate, 43) 1,5-naphthalenedisulfonate, 44) 2,6-naphthalenedisulfonate, 45) 2, 7- Naphthalenedisulfonate, 46) anthraquinone-1,5-disulfonate, 47) anthraquinone-1,8-disulfonate, 48) anthraquinone-2,6-disulfonate, 49) 9,10-dimethoxyanthracene-2,6- Salts of disulfonates such as disulfonate, 50) 9,10-diethoxyanthracene-2,6-disulfonate, and 2 equivalents of onium salt cation can also be used.

The onium salt sulfonate preferably used in the present invention is obtained by mixing the corresponding Cl ^- salt or the like in a mixed solvent of sulfonic acid or sodium or potassium sulfonate and water, or a mixed solvent of a hydrophilic solvent such as alcohol and water. It can be obtained by performing salt exchange together. The onium compound can be synthesized by a known method,
For example, Maruzen / New Experimental Chemistry Course 14-I, Chapter 2.3 (p.448), and Volume 14-III, Chapter 8.16 (p.18)
38), Chapter 7-14 (p. 1564); W. Kn
apczyk et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 91
Vol., 145 (1969); L. Maycok et al., Journal of Organic Chemistry (J. Or
g. Chem. 35, 2532 (1970);
V. Crivello et al., Polymer Chemistry Edition (Polym. Chem. Ed.), Vol. 18,
2677 (1980); U.S. Pat. No. 2,807,648.
Nos. 4,247,473 and JP-A-53-473.
Compounds can be synthesized by the methods described in JP-B Nos. 101331 and 5-53166. Preferred examples of the onium salt sulfonate which is favorably used as an acid generator in the present invention are shown below.

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In the present invention, these acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 25% by weight, more preferably 0.5 to 25% by weight, based on the total solid content of the image recording material.
It is added to the image recording material of the present invention at a ratio of 20% by weight. When the amount is less than 0.01% by weight, no image is obtained, and when the amount is more than 50% by weight, non-image areas are stained at the time of printing. . These compounds may be used alone or in combination of two or more.

[(B) Crosslinking Agent] The crosslinking agent that can be used in the present invention will be described. Examples of the crosslinking agent preferably used in the present invention include the following. (I) an aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) an epoxy compound These will be described in detail. I do. (I) Examples of the aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group include an aromatic compound and a heterocyclic compound poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. . However, it does not include resinous compounds obtained by polycondensing phenols and aldehydes known as resol resins under basic conditions. Although the resole resin is excellent in crosslinkability, it does not have sufficient thermal stability. In particular, when the resol resin is contained in a photosensitive material and stored at a high temperature for a long period of time, uniform development becomes difficult, which is not preferable.

Among aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, a compound having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group may be mentioned as a preferred example. it can. In the case of an alkoxymethyl group, the alkoxymethyl group is preferably a compound having 18 or less carbon atoms. Particularly preferred examples include compounds represented by the following general formulas (1) to (4).

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In the general formulas (1) to (4), L _{1 to} L
₈ independently represents a hydroxymethyl group or an alkoxymethyl group substituted with an alkoxy group having 18 or less carbon atoms, such as methoxymethyl and ethoxymethyl. These are preferred because they have high crosslinking efficiency and can improve printing durability. The crosslinking compounds exemplified above may be used alone or in combination of two or more.

(Ii) Compounds having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group are disclosed in European Patent Publication (hereinafter referred to as EP-A
No. 0,133,216, West German Patent No. 3,
Nos. 634,671 and 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP-
A, No. 0,212,482, and the like. More preferred examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred.

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent No. 1,539,192.

The crosslinking agents (i) to (iii) which can be used in the present invention are 5 to 80% by weight, preferably 10 to 75% by weight, more preferably 10 to 75% by weight, based on the total solids of the image recording material. Ranges from 20 to 70% by weight. If the amount of the crosslinking agent is less than 5% by weight, the durability of the photosensitive layer of the resulting lithographic printing plate precursor will be deteriorated. If it exceeds 80% by weight, it is not preferable from the viewpoint of storage stability. .

(Iv) In the present invention, it is also preferable to use a phenol derivative represented by the following general formula (5) as a crosslinking agent.

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In the general formula (5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the viewpoint of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred examples of the substituent include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, and a trifluoromethyl group. Is mentioned. Because of high sensitivity, Ar ¹ includes an unsubstituted benzene ring and a naphthalene ring, or a halogen atom,
Hydrocarbon groups or less, alkoxy groups having 6 or less carbon atoms,
A benzene ring and a naphthalene ring each having, as a substituent, an alkylthio group or a nitro group having 6 or less carbon atoms are particularly preferable. In the general formula (5), R ¹ and R ² may be the same or different, and each represents a hydrogen atom or a carbon atom.
Represents two or less hydrocarbon groups. It is particularly preferred that R ¹ and R ² are a hydrogen atom or a methyl group because of easy synthesis. R ³ is a hydrogen atom or a carbon atom
Or less hydrocarbon groups. Because of the high sensitivity,
R ³ is particularly preferably a hydrocarbon group having 7 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, and a benzyl group. m represents an integer of 2 to 4. n represents an integer of 1 to 3.

Specific examples of the phenol derivative represented by the general formula (5) preferably used in the present invention are shown below (crosslinking agents [KZ-1] to [KZ-8]). It is not limited to.

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These phenol derivatives can be synthesized by a conventionally known method. For example, [KZ-1] reacts phenol, formaldehyde, and a secondary amine such as dimethylamine and morpholine to form tri (dialkylaminomethyl) phenol, and then reacts with acetic anhydride.
Further, by reacting with ethanol in the presence of a weak alkali such as potassium carbonate, the compound can be synthesized by a route represented by the following reaction formula [1].

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Further, it can be synthesized by another method. For example, [KZ-1] is obtained by reacting phenol with formaldehyde or paraformaldehyde in the presence of an alkali such as KOH to give 2,4,6-trihydroxymethylphenol, and then reacting with ethanol in the presence of an acid such as sulfuric acid. Thus, the compound can also be synthesized by the route shown in the following reaction formula [2].

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These phenol derivatives may be used alone or in combination of two or more. In addition, when synthesizing these phenol derivatives, the phenol derivatives may be condensed with each other to produce by-products such as dimers and trimers. However, these phenol derivatives may be used while containing these impurities. Incidentally, even in this case, the impurity is 30%.
% Or less, and more preferably 20% or less.

In the present invention, the phenol derivative accounts for 5 to 70% by weight, preferably 1% by weight, based on the solid content of the image recording material.
It is used in an amount of 0 to 50% by weight. Here, if the addition amount of the phenol derivative as a cross-linking agent is less than 5% by weight, the film strength of the image portion at the time of image recording is deteriorated, and if it exceeds 70% by weight, the stability during storage is reduced. It is not preferable in respect of the point.

[(C) Alkali-soluble polymer] In the present invention
The (c) alkali-soluble polymer used is a polymer
Has the following acid group structure in the main chain or side chain of the compound
Points to something. Phenolic hydroxyl group (-Ar-OH),
Rubonic acid group (-CO_ThreeH), sulfonic acid group (-SO
_ThreeH), phosphate group (-OPO_ThreeH), sulfonamide group
(-SO _TwoNH-R), substituted sulfonamide-based acid groups (active
Imide group) (-SO_TwoNHCOR, -SO_TwoNHSO
_TwoR, -CONHSO_TwoR). Here, Ar represents a substituent
Represents a divalent aryl group which may be possessed, wherein R is a substituent
Represents a hydrocarbon group which may have Above all, preferred
(B-1) a phenolic hydroxyl group, (b)
-2) sulfonamide group and (b-3) active imide group.
Especially (b-1) having a phenolic hydroxyl group.
Molecular compounds are preferably used.

(B-1) Examples of the high molecular compound having a phenolic hydroxyl group include a condensation polymer of phenol and formaldehyde (hereinafter referred to as "phenol formaldehyde resin") and a degeneration of m-cresol and formaldehyde. (Hereinafter referred to as "m-cresol formaldehyde resin"), a condensation polymer of p-cresol and formaldehyde, a condensation polymer of m- / p-mixed cresol and formaldehyde, phenol and cresol (m-, p- , Or m- / p-mixture)
Novolak resins such as polycondensates of formaldehyde and
And a condensation polymer of pyrogallol and acetone. Alternatively, a copolymer obtained by copolymerizing a monomer having a phenol group in a side chain can be used.
Examples of the monomer having a phenol group include acrylamide, methacrylamide, acrylate, methacrylate, and hydroxystyrene having a phenol group. Specifically, N- (2-
(Hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- ( 4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene, m -Hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl acrylate, - (4-hydroxyphenyl) ethyl acrylate, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl)
Ethyl methacrylate and the like can be suitably used. The weight average molecular weight of the polymer is 5.0 × 10 ^{2 to} 2.0
× 10 ⁴ , number average molecular weight 2.0 × 10 ^{2 to} 1.0 × 1
0 ⁴ ones are preferred in view of image forming properties. These resins may be used alone or in combination of two or more. When they are combined, they have 3 to 8 carbon atoms, such as a condensation polymer of t-butylphenol and formaldehyde or a condensation polymer of octylphenol and formaldehyde as described in U.S. Pat. No. 4,123,279. A condensation polymer of phenol and formaldehyde having an alkyl group as a substituent may be used in combination.

The high molecular compound having a phenolic hydroxyl group preferably has a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000. Further, as described in U.S. Pat. No. 4,123,279, a condensate of phenol having a C3-8 alkyl group as a substituent and formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. May be used in combination. These polymer compounds having a phenolic hydroxyl group may be used alone or in combination of two or more.

(B-2) The polymer compound having a sulfonamide group has a monomer having a sulfonamide group as a main component. Examples of the monomer having a sulfonamide group include a monomer comprising a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule and a low-molecular compound having at least one polymerizable unsaturated bond. Is mentioned. Among them, a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable. Examples of such compounds include compounds represented by the following general formulas (1) to (5).

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In the formula, X¹And X^TwoAre independently-
O- or -NR²⁷Represents-. R^{twenty one}And R^{twenty four}Respectively
Independently a hydrogen atom or -CH_ThreeRepresents R^{twenty two}, R^{twenty five},
R²⁹, R ³²And R³⁶Are each independently having a substituent
An alkylene group having 1 to 12 carbon atoms which may be
Represents a kylene group, an arylene group or an aralkylene group. R
^{twenty three}, R²⁷And R³³Are each independently a hydrogen atom, a substituent
An alkyl group having 1 to 12 carbon atoms which may have
Represents a loalkyl group, an aryl group or an aralkyl group. Ma
R²⁶And R³⁷Each independently has a substituent
An alkyl group having 1 to 12 carbon atoms, cycloalkyl
Represents an aryl group or an aralkyl group. R²⁸, R³⁰
And R³⁴Are each independently a hydrogen atom or -CH_ThreeThe table
You. R³¹And R³⁵Is independently a single bond or substituted
An alkylene group having 1 to 12 carbon atoms which may have a group,
Cycloalkylene group, arylene group or aralkylene group
Represents Y^ThreeAnd Y^FourAre each independently a single bond, or
Represents -CO-.

Specifically, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be suitably used.

(B-3) The polymer compound having an active imide group has an active imide group represented by the following formula in the molecule, and the main monomer constituting the polymer compound, the active imide, As the monomer having a group,
In one molecule, a monomer composed of a low molecular compound having at least one active imide group represented by the following formula and at least one polymerizable unsaturated bond is exemplified.

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As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylamide, N
-(P-Toluenesulfonyl) acrylamide and the like can be suitably used.

The alkali-soluble polymer used in the present invention is
It is not necessary to consist of one kind selected from monomers having an acidic group of (b-1) to (b-3), and two or more kinds of monomers having the same acidic group or monomers having different acidic groups may be used. Those obtained by copolymerizing two or more kinds can also be used. As a copolymerization method, a conventionally known graft copolymerization method, block copolymerization method, random copolymerization method, or the like can be used.

The copolymer is copolymerized (b-1)
It is preferable that the monomer having the acidic group of (b-3) is contained as a copolymer component in an amount of 10 mol% or more, more preferably 20 mol% or more. (B-1)
If the amount of the monomer (b-3) containing an acidic group is less than 10 mol%, the effect of improving the development latitude will be insufficient.

The copolymer (b-1)
A monomer other than the monomer having an acidic group of (b-3) may be contained as a copolymerization component. Examples of other monomers that can be used as a copolymer component include:
The following monomers (1) to (12) are exemplified.

(1) Acrylic esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and methacrylic esters. (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylates such as acrylates; (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl Alkyl methacrylates such as methacrylate. (4) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-
Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-
Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, and N-ethyl-N-phenylacrylamide. (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether. (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate. (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (12) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid;

In the present invention, as the alkali-soluble polymer, those having a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more are preferable irrespective of a homopolymer or a copolymer in view of film strength. More preferably, the weight average molecular weight is 5,000 to 300,000, and the number average molecular weight is 800
２５０250,000 and a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.1 to 10.

In the above copolymer, (b-1) to (b)
The compounding weight ratio of the monomer having an acidic group of (3) to another monomer is preferably in the range of 50:50 to 5:95 from the viewpoint of development latitude, and is preferably in the range of 40:60 to 10:90. Are more preferable.

Each of these alkali-soluble polymers may be used alone or in combination of two or more kinds. The total solid content of the image recording material is 30 to 99% by weight, preferably 40 to 95% by weight, and particularly preferably 40 to 95% by weight. Preferably 50 to 90
It is used in a weight% addition amount. If the amount of the alkali-soluble polymer is less than 30% by weight, the durability of the photosensitive layer deteriorates, and if it exceeds 99% by weight, both sensitivity and durability are not preferred.

[Other Components] In the present invention, the above-mentioned four components are essential, but if necessary, various compounds may be added in addition to these. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orient Chemical Industrial Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253)
5), ethyl violet, rhodamine B (CI145
170B), malachite green (CI42000),
Methylene blue (CI52015) and the dyes described in JP-A-62-293247 are exemplified. These dyes are preferably added because the image area and the non-image area can be easily distinguished after image formation.
Incidentally, the addition amount is 0.0% with respect to the total solid content of the image recording material.
It is a ratio of 1 to 10% by weight.

Further, in the negative type image recording material of the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to widen the stability of processing under development conditions.
Non-ionic surfactants described in JP-A-59-121044, and amphoteric surfactants described in JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-
Examples thereof include carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.). The ratio of the nonionic surfactant and the amphoteric surfactant in the image recording material is 0.05 to 15%.
% By weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the image recording material of the present invention, if necessary, for imparting flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid And polymers. In addition to these, epoxy compounds, vinyl ethers and the like may be added.

The image recording material of the present invention having the above constitution can be suitably used for a lithographic printing plate precursor. Hereinafter, a lithographic printing plate precursor using the image recording material of the present invention will be described. In this specification, a lithographic printing plate precursor refers to a plate material in which an image forming pattern of an ink receiving portion and a non-ink receiving portion is not formed, and a lithographic printing plate is a non-ink receiving portion and a non-ink receiving portion. FIG. 4 shows a plate material in a state where an image pattern of an ink receiving portion is formed and is ready for printing.

The lithographic printing plate precursor has, on a support, a photosensitive layer containing the image recording material of the present invention and, if necessary, other layers. The photosensitive layer can be usually produced by dissolving each of the above components in a solvent and coating the solution on a suitable support. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate,
N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, water and the like, but are not limited thereto. . These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The amount of coating on the support obtained after coating and drying (solid content)
Although it depends on the intended use, the lithographic printing plate material is generally preferably from 0.5 to 5.0 g / m ² . As a method of applying, various methods can be used. For example, bar coater application, spin coating, spray application, curtain application, dip application, air knife application,
Examples include blade coating and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive layer deteriorate.

In the photosensitive layer, a surfactant for improving coating properties, for example, a fluorine-based surfactant as described in JP-A-62-170950 can be added. . The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 1% by weight based on the total solid content of the photosensitive layer.
0.5% by weight.

The support used in the present invention is a dimensionally stable plate-like material, such as paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), the above-mentioned metal-laminated or vapor-deposited paper, or plastic film.

As the support used in the present invention, a polyester film or an aluminum plate is preferable. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The different elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth,
There are 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 is pure aluminum, but 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 is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate is approximately 0.1 to
It is about 0.6 mm, preferably 0.15 to 0.4 mm, more preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed to remove rolling oil on the surface. The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening the surface, or a method of chemically selecting the surface It is performed by a method of dissolving. As the mechanical method, a ball polishing method, a brush polishing method,
Known methods such as a blast polishing method and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary,
If desired, anodizing treatment is performed to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions cannot be specified without fail because they vary depending on the electrolyte used.
A solution having an electrolyte concentration of 1 to 80% by weight and a liquid temperature of 5 to 70%
° C, current density 5-60 A / dm ² , voltage 1-100 V,
An electrolysis time of 10 seconds to 5 minutes is appropriate. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. So-called "scratch dirt" tends to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. As the hydrophilization treatment, US Pat.
No. 066, No. 3,181,461, No. 3,280,
There is an alkali metal silicate (for example, an aqueous solution of sodium silicate) as disclosed in the specifications of Nos. 734 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,461,
For example, a method of treating with polyvinyl phosphonic acid as disclosed in each specification of JP-A-4,689,272 is used.

In the lithographic printing plate precursor, an undercoat layer can be provided on the support, if necessary. As the undercoat layer component, various organic compounds are used, for example,
Carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, and methylene diphosphonic which may have a substituent Acids and organic phosphonic acids such as ethylene diphosphonic acid, optionally substituted phenylphosphoric acid, naphthyl phosphoric acid, organic phosphoric acids such as alkyl phosphoric acid and glycerophosphoric acid, optionally substituted phenylphosphinic acid Organic phosphinic acids such as naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine. And two or more kinds may be used in combination. The coating amount of the undercoat layer is 2 to 200 m
g / m ² is appropriate. As described above, a lithographic printing plate precursor using the image recording material of the present invention can be manufactured.

Hereinafter, the exposure and development processes will be described.
The obtained lithographic printing plate precursor has a wavelength of 760 to 1200 n.
The image is exposed by a solid-state laser and a semiconductor laser that emit m infrared rays. In the present invention, the development treatment may be performed immediately after the laser irradiation, but it is preferable to perform the heat treatment between the laser irradiation step and the development step. The heat treatment is preferably performed at a temperature of 80 to 150 ° C. for 10 seconds to 5 minutes. By this heat treatment, at the time of laser irradiation,
The laser energy required for recording can be reduced.

After performing a heat treatment as required, the lithographic printing plate precursor is developed with an alkaline aqueous solution.
As the developer and replenisher used for the lithographic printing plate precursor, conventionally known aqueous alkali solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents may be used alone or in combination of two or more. Particularly preferred developers among these alkaline agents are sodium silicate,
It is an aqueous solution of a silicate such as potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate.
No. 4 and JP-B-57-7427 are effectively used.

In the case of further developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It is known that a large amount of lithographic printing plate precursors can be processed without replacing the developing solution in the developing tank for a long period of time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as needed for the purpose of promoting or suppressing the developing property, dispersing the developing residue and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and hydrogen sulfite; an organic carboxylic acid; an antifoaming agent; Agents can also be added. The lithographic printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally consists of a developing section and a post-processing section, and consists of a device for transporting a printing plate material, each processing solution tank, and a spray device. Each developing solution is sprayed from a spray nozzle to perform a developing process. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such automatic processing,
Processing can be performed while replenishing each processing solution with a replenisher according to the processing amount, operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The planographic printing plate obtained as described above is
After applying the desensitized gum as desired, it can be subjected to a printing process. However, when a lithographic printing plate having a higher printing durability is desired, a burning treatment is performed. In the case of burning a lithographic printing plate, prior to burning, the lithographic printing plate may be burned prior to burning.
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 1859 and 61-159655. As the method, a method of applying the printing solution on a lithographic printing plate with a sponge or absorbent cotton impregnated with the surface conditioning solution, or immersing the printing plate in a vat filled with the surface conditioning solution, Application by an automatic coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. In general, it is appropriate that the application amount of the surface conditioning liquid is 0.03 to 0.8 g / m ² (dry weight).

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then heated at a high temperature using a burning processor (eg, a burning processor: BP-1300 sold by Fuji Photo Film Co., Ltd.). Heated. The heating temperature and time in this case depend on the type of the component forming the image, but are preferably in the range of 100 to 300 ° C. and 1 to 20 minutes. The burning-processed lithographic printing plate can be subjected to a conventional treatment such as washing with water and gumming if necessary, but a surface-regulating solution containing a water-soluble polymer compound or the like is used. In such a case, the so-called desensitization treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0228]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. (Example 1) [Preparation of substrate] An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased. And washed well with water. This aluminum plate was etched by immersing it in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, a 3 g / m ² direct current anodic oxide film was formed on the aluminum plate at a current density of 15 A / dm ² using 7% sulfuric acid as an electrolytic solution, followed by washing with water and drying.
The coating was dried at 90 ° C. for 1 minute. The coating amount of the dried coating film was 10 mg / m ² .

-Composition of undercoat liquid-β-alanine ... 0.5 g methanol ... 95 g water ...・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5g

[Preparation of Lithographic Printing Plate Precursor]-Composition of photosensitive solution-Acid generator X-1 (the following structural formula) 0.15 g Table 1 below 0.10 g Novolak resin obtained from phenol and formaldehyde 1.5 g (weight average molecular weight 10,000) Crosslinking agent MM-1 (the following structural formula) 0.50 g Fluorosurfactant 0.03 g (MegaFac F- 177, manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 15 g 1-methoxy-2-propanol・ ・ ・ ・ ・ ・ ・ 10g Methyl alcohol ・ ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ 5g

[0231]

Embedded image

This photosensitive solution was applied to the above substrate as a support and dried at 100 ° C. for 1 minute to obtain a lithographic printing plate precursor of Example 1. The coating weight after drying was 1.3 g / m ² .

(Examples 2 to 15) The procedure of Example 1 was repeated, except that the anionic infrared absorber used in the photosensitive solution was changed to the anionic infrared absorbers shown in Tables 1 and 2. Thus, planographic printing plate precursors of Examples 2 to 15 were obtained.

Comparative Examples 1 and 2 In Example 1, except that the anionic infrared absorbent used in the photosensitive solution was replaced by infrared absorbents B-1 and B-2 represented by the following structural formulas, In the same manner as in Example 1, lithographic printing plate precursors of Comparative Examples 1 and 2 were obtained.

[0235]

Embedded image

<Evaluation of Sensitivity and Development Latitude> As shown in Tables 1 and 2 below, the lithographic printing plate precursors of Examples 1 to 15 and Comparative Examples 1 and 2 were used as semiconductor lasers having a wavelength of 840 nm or 1064 nm. Exposure was performed using a YAG laser. Which laser is used was appropriately selected according to the absorption wavelength of the infrared absorbing dye contained therein. After the exposure, a heat treatment was performed for 1 minute in an oven at 140 ° C., followed by a developer DP-4 and a rinse FR- manufactured by Fuji Photo Film Co., Ltd.
3 (1: 7) was developed using an automatic processor ("PS Processor 900VR", manufactured by Fuji Photo Film Co., Ltd.). Two levels of developer DP-4 were prepared, one diluted 1: 6 and one diluted 1:12. DP above
The line width of the non-image part obtained with the developer diluted 1: 6 of -4 was measured, and the irradiation energy of the laser corresponding to the line width was determined and used as an index of sensitivity (mJ / cm ² ). . The smaller the measured value (mJ / cm ² ), the higher the sensitivity of the lithographic printing plate.

Next, the line width of the non-image portion obtained with the standard developer diluted 1: 6 and the diluted developer diluted 1:12 was measured, and the line width corresponding to the line width was measured. The irradiation energy of the laser to be used was determined, and the difference between the two sensitivities was used as an index of the development latitude. The smaller the difference is, the better the development latitude is, and if it is 20 mJ / cm ² or less, it is at a practical level.

<Evaluation of Storage Stability> The lithographic printing plate precursors of Examples 1 to 15 and Comparative Examples 1 and 2 were stored for 3 days in a high-temperature and high-humidity environment at a temperature of 45 ° C. and a humidity of 75% RH.
Laser exposure and development were carried out in the same manner as described above, the sensitivity was determined in the same manner, the difference was compared with the above results, and the difference was determined, which was used as an index of storage stability. If the fluctuation of the sensitivity is 20 mJ / cm ² or less, the storage stability is good and is at a practical level. Tables 1 and 2 show the evaluation results.

[0239]

[Table 1]

[0240]

[Table 2]

From the above results, the lithographic printing plate precursors of Examples 1 to 15 were compared with the lithographic printing plate precursors of Comparative Examples 1 and 2.
It can be seen that the sensitivity to infrared laser is high, and the difference between the sensitivities when the above two levels of developer is used is extremely small, and that the developer has a sufficiently practical development latitude. Further, the lithographic printing plate precursors of Examples 1 to 15 were all compared with the lithographic printing plate precursors of Comparative Examples 1 and 2.
The sensitivity fluctuation before and after storage is extremely small, the storage stability is excellent, and it satisfies a sufficiently practical level.

[0242]

According to the present invention, it is possible to directly make a plate by recording from digital data of a computer or the like using a solid-state laser and a semiconductor laser that emit infrared light. In addition, it is possible to provide an image recording material having good development latitude and storage stability.

Continued on front page F term (reference) 2H025 AA01 AA04 AA11 AC08 AD01 CB42 CC11 CC17 2H096 AA06 BA06 EA04 2H114 AA04 AA24 BA01 BA05 BA10 DA03 DA22 DA23 DA24 DA31 DA34 DA39 DA49 DA52 EA02 EA10 GA03 GA04 GA08 GA09

Claims (1)

[Claims] 1. An image recording material comprising at least the following (a) to (d): (A) a compound that decomposes by light or heat to generate an acid (b) a crosslinking agent that crosslinks with an acid (c) a polymer compound that is insoluble in water and soluble in an aqueous alkaline solution (d) Anionic infrared absorbent represented by (I) (In the general formula (I), M represents a conjugated chain, G _a ^- represents an anionic substituent, G _b represents a neutral substituent .X
^{m +} represents a hydrogen ion or an m-valent cation;
Represents an integer of 6. )