JP2000075474A - Image forming material and planographic printing original plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet ray-sensitive image forming material excellent in sensitivity, developing latitude and storage stability and to provide a planographic printing original plate using the material and capable of forming an image with high sensitivity by using infrared rays for direct plate making. SOLUTION: This infrared ray-sensitive image forming material contains a cationic infrared ray-absorbable framework and an anionic infrared ray- absorbable framework in one molecule. When the image forming material is used as a positive type, (b) a polymer compound, which is insoluble in water but soluble in aqueous alkaline solution, is further added to the material, and when the image forming material is used as a negative type, (c) a compound capable of forming an acid by heating and (d) an acid-crosslinkable compound together with (b) are added to the material. The objective planographic printing original plate can be produced by providing an image forming layer by using the image forming material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material suitable as a positive or negative type image forming material and a lithographic printing plate precursor using the same. In particular, it is writable by heat of an infrared laser, a thermal head or the like. An image forming material capable of forming both positive type and negative type images with an infrared laser, and a lithographic printing method using the same, which is particularly suitable for a lithographic printing plate precursor for so-called direct plate making that can directly make a plate from a digital signal of a computer or the like. Regarding the original plate.

[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 has been paid to those using these infrared lasers.
A positive type lithographic printing plate material for infrared laser for direct plate making is disclosed in JP-A-7-285275.
The present invention is an image recording material in which a substance that absorbs light and generates heat and a positive photosensitive compound such as quinonediazide compounds are added to an aqueous alkaline solution-soluble resin,
In the image area, the positive photosensitive compound acts as a dissolution inhibitor to substantially lower the solubility of the aqueous alkali-soluble resin, and in the non-image area, it is decomposed by heat and no longer exhibits the dissolution inhibiting ability, and is removed by development. To form an image.

As a result of studies by the present inventors, it has been found that a positive image can be obtained without adding a quinonediazide compound to an image recording material. There is a drawback that the stability of the sensitivity to the concentration of the developing solution, that is, the development latitude is deteriorated.

On the other hand, it is known that onium salts and alkali-insoluble compounds capable of hydrogen bonding have an alkali dissolution inhibiting action of alkali-soluble polymers. WO097 / 39894 describes a composition using a cationic infrared-absorbing dye as a dissolution inhibitor of an alkali-water-soluble polymer as such a positive-type infrared laser-compatible image forming material. This positive action is such that the cationic infrared absorbing dye absorbs the laser light and the heat generated thereby eliminates the dissolution suppressing effect. In this case, since no cationic dye is present as an infrared absorber, the absorbance is low, so that the on-off of the alkali development in the exposed / unexposed areas is difficult to obtain and a good image cannot be obtained (low sensitivity, development The latitude is narrow). Here, the development latitude refers to an allowable range in which a good image can be formed when the alkali concentration of the alkali developer is changed.

On the other hand, as a negative-type image recording material recordable with an infrared laser, a recording material comprising an onium salt, a resole resin, a novolak resin, and an infrared absorber described in JP-A-7-20629. is there. 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 rays is converted into thermal energy by an infrared absorber, and the onium salt is decomposed by the heat. An image is formed by the above-mentioned process, that is, an image is recorded, that is, a plate is made of a recording material by accelerating a cross-linking reaction between a cross-linking agent and a binder which are cross-linked by an acid generated by decomposition of an onium salt. It is. But,
In this case, the infrared dye used was only a cationic dye, and the amount of heat generated by exposure was small, so that there was a problem in sensitivity.

As described above, the infrared absorbing dye used in the infrared laser-compatible image forming material includes (1) a cationic dye and a dye having a counter anion having no absorption in the infrared region.
Alternatively, the method is limited to (2) an anionic dye and a dye having a counter cation having no absorption in the infrared region. For this reason, the absorbance as one molecule was low, and the absorption region was short. For this reason, it was not possible to write data from light sources having greatly different wavelengths, for example, from both a semiconductor laser and a solid-state laser such as a YAG laser.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an infrared-sensitive image-forming material which can be written with an infrared laser having high sensitivity and good development latitude and storage stability. Another object of the present invention is to provide a lithographic printing plate precursor capable of forming an image with high sensitivity using an infrared laser for direct plate making.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies for the purpose of increasing the image forming property, that is, the sensitivity and the development latitude, and as a result, a structure in which both the cation portion and the anion portion absorb infrared rays. It has been found that by using a specific ionic dye having a sensitizing property, development latitude is improved without being exposed even under a white light, and that the present invention can be applied to both positive and negative types. Was completed. That is, the infrared laser-sensitive image forming material of the present invention is characterized in that one molecule contains an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule.

The infrared laser-sensitive image forming material according to claim 2 of the present invention comprises (a) an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule, and (b) water. And a polymer compound insoluble in an aqueous alkaline solution.

The infrared laser-sensitive image forming material according to claim 3 of the present invention comprises: (a) an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule; and (b) water. It is characterized by containing a polymer compound that is insoluble and soluble in an aqueous alkali solution, (c) a compound that generates an acid by heat, and (d) a compound that crosslinks using an acid as a catalyst.

The lithographic printing plate precursor according to the present invention is provided on a support,
An image forming layer comprising the image forming material according to any one of claims 1 to 3 is provided.

Although the function of the present invention is not clear, the ionic dye according to the present invention, which has a skeleton that absorbs infrared rays in both the cation portion and the anion portion, has a particularly high absorbance and a wide absorption region due to its structure. It has the characteristic of having. Therefore, it is considered that a large amount of heat is generated by the exposure, and a highly sensitive image forming material can be obtained. At the same time, light sources having greatly different wavelengths (for example, a 830 nm semiconductor laser and
(064 nm YAG laser) has also been found to be possible.

Since the ionic dye of the present invention has a skeleton that absorbs infrared rays in both the cation portion and the anion portion, the image forming material of the present invention can be used as a positive image forming material or a negative image forming material. Can also be used as That is, when used as a positive photosensitive material, the cationic infrared absorbing dye portion of the ionic dye functions as a dissolution inhibitor for the alkali water-soluble polymer. The dye of the present invention
Since the absorbance is higher and the heat generated by exposure is higher than conventional dyes, the dissolution inhibiting action is efficiently released, and a photosensitive material with high sensitivity can be obtained. Further, when used as a negative photosensitive material together with an acid generator and a crosslinking agent that is crosslinked by an acid, the dye of the present invention generates a larger amount of heat upon exposure than conventional dyes, so that the thermal acid generator can efficiently use the acid. Can be generated. Therefore, the acid-catalyzed crosslinking reaction proceeds efficiently, and a photosensitive material with higher sensitivity than before can be obtained.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention is characterized in that a specific ionic dye having a cationic dye skeleton and an anionic dye skeleton in one molecule is used, but when the image forming material of the present invention is used as a positive type, the above-mentioned ( a) With a specific ionic dye,
(B) It is a preferable embodiment to use a water-insoluble and alkaline water-soluble polymer compound. When used as a negative type, in addition to the above (a) and (b),
It is desirable to use (c) a compound that generates an acid by heat and (d) a compound that crosslinks using an acid as a catalyst.

Hereinafter, the main compounds used in the image forming material of the present invention will be sequentially described. [(A) Ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule] In the present invention, (a) an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule The anionic infrared absorbing skeleton in a dye (hereinafter, appropriately referred to as an ionic dye) refers to a dye having substantially no anionic structure in a nucleus of the dye that substantially absorbs infrared light and having an anionic structure. The term "anionic infrared absorbing skeleton" as used herein refers to a dye having substantially no anionic structure in the mother nucleus of the dye that substantially absorbs infrared light and having an anionic structure. For example, (1) anionic metal complex, (2) anionic carbon black,
(3) Anionic phthalocyanine and (4) a compound represented by the following general formula (I).

[0016]

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[0017] In the formula, M represents a conjugated chain, G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +}
Represents a 1- to m-valent cation containing a proton, where m
Represents an integer of 1 or 6.

Here, (1) the anionic metal complex refers to an anion in which the central metal and the ligand of the complex part that substantially absorbs light become anions. (2) Examples of the anionic carbon black include those having an anionic group such as sulfonic acid, carboxylic acid, or phosphonic acid group as a substituent. To introduce these groups into carbon black,
Carbon Black Handbook 3rd Edition (edited by The Carbon Black Association, April 5, 1995, published by The Carbon Black Association)
As described on page 12, means such as oxidation of carbon black with a predetermined acid may be employed. (3) Anionic phthalocyanine refers to an anion as a whole to which the above-mentioned anionic group is bonded as a substituent. Further, in the compound (4) represented by the general formula (I), M in the general formula (I) represents a conjugated chain, and the conjugated chain may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

[0019]

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In the formula, R ^{n to} R ^{2n + 1} 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, a thio group, a sulfonyl group, a sulfinyl group. , An oxy group, or an amino group, which may be linked to each other to form a ring structure. n shows the integer of 1-8.

[0021] G _a ^- represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a 1- to m-valent cation containing a proton, wherein m represents an integer of 1 or 6.

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

These alkyl groups may have a substituent, and a monovalent nonmetallic atomic group except hydrogen is used as the substituent. Preferred examples include a halogen atom (-F, -Br, -Cl, -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-
An arylureido group, an N′-aryl-N-alkylureido group, an 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 Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, and the like A conjugate base group (hereinafter referred to as “carboxylate”), an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, N, N- Diarylcarbamoyl group, N-alkyl-N - (. Hereinafter referred to as "sulfonato group") arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group, alkoxy sulfonyl group, arylene Roxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-aryl Sulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N- Arylsulfamoyl group, N-acylsulfamoy Group and its conjugated 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, Ar represents an aryl group) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ R, R Represents an alkyl group) and its conjugate base group, an N-arylsulfonylcarbamoyl group (—CONHSO ₂ Ar, Ar represents an aryl group), its conjugate base group, and an alkoxysilyl group (—Si (OR) _3. , R represents an alkyl group), an aryloxysilyl group (—Si (OAr) ₃ ,
Ar represents an aryl group. ), Hydroxysilyl group (-
Si (OH) ₃₎ and its conjugated base group, a phosphono group (one PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as "phosphonato group".), A dialkyl phosphono group (-PO
₃ R ₂ and R represent an alkyl group. ), A diarylphosphono group (—PO ₃ Ar ₂ , Ar represents an aryl group),
Alkylarylphosphono group (—PO ₃ (R) (A
r) and R represent an alkyl group and Ar represents an aryl group. ) Monoalkyl phosphono group (-PO ₃ H (R), R represents an alkyl group.) And its conjugated base group (hereinafter. Referred to as "alkylphosphonato group"), monoaryl phosphono group (-PO ₃ H (Ar) and Ar represent an aryl group) and its conjugate base group (hereinafter, referred to as “arylphosphonate group”), phosphonooxy group (—OPO ₃ H ₂ ), and its conjugate base group (hereinafter, “phosphonatooxy group”). Group "), a dialkylphosphonooxy group (-OPO
₃ (R) ₂ and R represent an alkyl group. ), A diarylphosphonooxy group (—OPO ₃ (Ar) ₂ , Ar represents an aryl group), an alkylarylphosphonooxy group (—OPO ₃ (R) (Ar), R is an alkyl group, and Ar is an aryl A monoalkylphosphonooxy group (—OPO ₃ H (R), R represents an alkyl group) and its conjugate base group (hereinafter, referred to as “alkylphosphonatooxy group”), monoaryl. A phosphonooxy group (—O
PO ₃ H (Ar) Ar represents an aryl group. ) And its conjugate base group (hereinafter, referred to as “arylphosphonatooxy group”), cyano group, nitro group, aryl group, alkenyl group, and alkynyl group. Specific examples of the alkyl group in these substituents include the above-described alkyl group (I), and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and 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 group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group,
Examples include a phenoxynitrophenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group include an ethynyl group, -Propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like. Examples of the acyl group (R ¹ CO—) include a hydrogen atom for R ¹ and the above-described alkyl group, aryl group, alkenyl group, and alkynyl group.

Of these substituents, a halogen atom ((-F, -Br, -Cl,-
I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, 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 group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonate group, monoarylphosphono group, arylphosphonato group, phosphonooxy group , A phosphonatoxy group, an aryl group, an alkenyl group and the like.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably has 1 carbon atom
And C 12 to C 12, C 3 to C 12 branched and C 5 to C 10 cyclic alkylene groups. Preferred specific examples of the substituted alkyl group obtained by combining the substituent with an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, and an allyloxy group. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenyl Carbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycal Nylmethyl group, methoxycarbonylbutyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group ,
N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N
A -methyl-N- (phosphonophenyl) sulfamoyloctyl group,

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

When R ^{n to} R ^{2n + 1} are an aryl group, the aryl group is one in which one to three benzene rings form a condensed ring, and a benzene ring and a five-membered unsaturated ring form a condensed ring. Specific examples include phenyl, naphthyl, anthryl, phenanthryl,
Examples thereof include an indenyl group, an acenabutenyl group, and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable.

As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferred substituents include the above-mentioned alkyl groups, substituted alkyl groups,
Examples of the substituent for the substituted alkyl group include those described above. Preferred specific examples of such a substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, and a trifluoromethylphenyl group. A hydroxyphenyl group, a methoxyphenyl group, a methoxyethoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylthiophenyl group, a tolylthiophenyl group, a phenylthiophenyl group, an ethylaminophenyl group, a diethylaminophenyl group, a morpholinophenyl group, Acetyloxyphenyl group, benzoyloxyphenyl group, N
-Cyclohexylcarbamoyloxyphenyl group, N-
Phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl Nyl, phosphonophenyl, phosphonatophenyl, diethylphosphonophenyl, diphenylphosphonophenyl, methyl, tolylphosphonatophenyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methyl Allylphenyl group, 2
-Methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

R ^{n to} R ^{2n + 1} alkenyl, substituted alkenyl, alkynyl, substituted alkynyl (—C
(R ⁷ ) = C (R ⁸ ) (R ⁹ ), and -C≡C
As (R ¹⁰ ), those in which R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are monovalent nonmetallic atomic groups can be used. Preferred R ⁷ , R ⁸ ,
Examples of R ⁹ and R ¹⁰ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. As specific examples thereof, those shown as the above examples can be similarly mentioned. Examples of preferred substituents of R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include a hydrogen atom, a halogen atom, and a C 1-10 carbon atom.
Linear, branched and cyclic alkyl groups. Specific examples of such R ^{n to} R ^{2n + 1} include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl Group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, allyl, 1-propenylmethyl, 2-butenyl, 2-methylallyl , 2-methylpropenyl group, 2-propynyl group, 2-
Butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylhenzyl group, 1-methyl-1-phenethyl group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group, phenoxydiethyl group,
Allyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, morpholinoethyl group, morpholinopropyl group, sulfopropyl group, sulfonatopropyl group, sulfobutyl group, sulfonatobutyl group / carboxymethyl group, carboxyethyl group, carboxypropyl group, Methoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, phenoxycarbonylmethyl group, methoxycarbonylpropyl group, N-methylcarbamoylethyl group, N, N-ethylaminocarbamoylmethyl group, N-phenylcarbamoylpropyl group, N-
Tolylsulfamoylbutyl group, p-toluenesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, phosphonoethyl group, phosphonopropyl group, p-phosphonobenzylaminocarbonylethyl group, phosphonatomethyl group, Examples include a phosphonate propyl group, a phosphonate butyl group, a p-phosphonato benzylaminocarbonylethyl group, a vinyl group, and an ethynyl group.

A substituted carbonyl group of R ^{n to} R ^{2n + 1} (R ¹¹ C
As O-), those in which R ¹¹ is a monovalent nonmetallic atomic group can be used. 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 aryl group in these include those exemplified as the above-described alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituents include a formyl group,
Acyl group, carboxyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, and even more preferred are formyl group, acyl group, alkoxycarbonyl group and aryl. And a roxycarbonyl group. Specific examples of preferred substituents include formyl group, acetyl group, benzoyl group, carboxyl group,
Methoxycarbonyl group, allyloxycarbonyl group, N
-Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted thio group (R ¹⁴ S-), those in which R ¹⁴ is a monovalent nonmetallic atomic group excluding hydrogen can be used. Preferred examples of the substituted thio group include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these alkyl groups Said aryl group, a substituted alkyl group, an aryl group, and can be those exemplified as the substituted aryl group, R ¹³ of the acyl group in the acylthio group (R ¹³ CO-) in As described above. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

As the substituted sulfonyl group (R ¹⁹ SO ₂ —), those in which R ¹⁹ is a monovalent nonmetallic atomic group can be used. More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those exemplified as the above-described alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

As the substituted sulfinyl group (R ¹⁸ SO—), those wherein R ¹⁸ is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, N
-Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group,
An N, N-diarylsulfinamoyl group and an N-alkyl-N-arylsulfinamoyl group are exemplified. Examples of the alkyl group and aryl group in these include those exemplified as the above-described alkyl group, substituted alkyl group, aryl group, and 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.

As the substituted oxy group (R ¹² O—), R ¹²
Is a monovalent non-metallic atomic group other than hydrogen. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy group. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Examples include a phosphonooxy group and a 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. Further, an acyl group (R ¹³ CO
Examples of —) include those in which R ¹³ has been exemplified as the aforementioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these substituents, 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, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group,
Examples include a cumenyloxy group, a methoxyphenyloxy group, an ethoxyphenyloxy group, a chlorophenyloxy group, a bromophenyloxy group, an acetyloxy group, a benzoyloxy group, a naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, and a phosphonatoxy group.

A substituted amino group (R ¹⁵ NH—, (R ¹⁶ ) (R
¹⁷ ) As N-), those in which R ¹⁵ , R ¹⁶ and R ¹⁷ are monovalent nonmetallic atomic groups other than hydrogen can be used.
Preferred examples of the substituted amino group include N-alkylamino, N, N-dialkylamino, N-arylamino, N, N-diarylamino, 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'
-A diarylureido group, an N'-alkyl-N'-arylureido group, an N-alkylureido group, an N-arylureido group, an N'-alkyl-N-alkylureido group, an N'-alkyl-N-arylureido group , N ',
An N′-dialkyl-N-alkylureido group, N ′,
N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N
-Arylureido group, N ', N'-diaryl-N-
Alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-
N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N- Examples include an 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 include the above-described alkyl group, substituted alkyl group, aryl group, and those exemplified as the substituted aryl group.
Acylamino group, N- alkylacylamino group, N- aryl - acyl group in acylamino group (R ¹³ CO
R13 ^in- ) is as described above. Of these, more preferred are N-alkylamino group, N, N
-Dialkylamino group, N-arylamino group, 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, an acetylamino group, and the like.

Further, in the general formula (I), G _a ^-
Represents an anionic substituent, G _b represents a neutral substituent, these may be respectively represented by the following structure.

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In the formula, L _{1 to} L ₄ each independently represent a hydrogen atom, a halogen, a cyano group and the above-mentioned alkyl, aryl, alkenyl, alkynyl, carbonyl,
Examples thereof include a thio group, a sulfonyl group, a sulfinyl group, an oxy group, and an amino group. L ₁ and L ₂ , and L ₃ and L ₄ may be linked to form a ring structure. G as a preference
_b acidic nucleus of the cyanine dye, also G _a ^- include those acidic nucleus is anionized. As the acidic nucleus, "Th
e teory of the Photograph
ic Process, p. 199, Tables 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-
4) Oxindole nucleus, for example, 1-alkyl-2,3, such as isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one.
-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 such as rhodanine and its derivatives, such derivatives include 3-
Examples include 3-alkyl rhodanines such as ethyl rhodanine and 3-allyl rhodanine, and 3-aryl rhodanines such as 3-phenyl rhodanine.

7) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione) nucleus, for example, 2-ethyl-2-thio-2,4-
Oxazolidinedione, 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-thiazolidinethione nucleus such as 2,4-thiazolidinedione
Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, 11) thiazolidinone nucleus such as 4-thiazolidinone,
3-ethyl-4-thiazolidinone,

12) 4-thiazolinone nucleus, for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, 13) 2-imino-2-oxozoline-4- On (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-imidazolidinione, 3-ethyl-2-thio-2,4-imidazolidinedione, 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 such as N-methyl-4-hydroxy-2 (1H) -Quinolinone, N-n-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, such as 5-methylthioindoxyl.

In the general formula (I), Z represents a chalcogen atom or a —C (Y ₁ ) (Y ₂ ) group. Where Y
₁ and Y ₂ may be the same or different;
_{2 R ', - SO 2 R} ' represents a '. R ′ and R ″ represent the same alkyl group and aryl group as described above.

Specific examples of the anionic infrared absorbing agent are shown below, but the present invention is not limited thereto.

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These can be synthesized by a known method. For example, the anionic Ni complex (AD-1 ⁻ , A
D-2 ^-) is the journal of the American Chemical Society (J.of American Chem.So
c. 88), 1966, pp. 43-50 or 48.
It can be synthesized according to the method described on pages 70-4875. In addition, the anionic carbon black (AD-3 ^-)
Is the Carbon Black Handbook (Carbon Black Association,
The carboxylic acid group is introduced by oxidation as described on page 12 of the Carbon Black Association of Japan (1995).

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

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Here, θ, α, and φ are variables, respectively.
The specific structure of the anionic dye skeleton can be shown by a combination of the respective partial structures G, θ, Mαφ, G, and θ. For example, the partial structures G _a1 , Mf3, G _b 2
Are as follows,

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

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Examples of the partial structure of the anionic dye skeleton of the present invention are shown below, but the present invention is not limited to these specific examples. Examples of the partial structures G and θ include the following.

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

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The following are examples of the methine chain Mαφ.

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When the methine chain Mαφ has a substituent, examples of the substituent φ-Y include the following.

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Next, the cationic dye skeleton will be described.
The term "cationic infrared dye skeleton" as used herein means a dye which has a cationic structure in a core which substantially absorbs infrared rays. Examples thereof include known dyes such as commercially available dyes and dyes described in literatures (for example, "Dye Handbook" edited by Organic Synthetic Chemistry Association, 1970). Specific examples include carbonium dyes, methine dyes, and cyanine dyes. , Aminium dyes, diimmonium dyes and the like.

Among these dyes, dyes whose light absorption maximum shifts to the longer wavelength side and which absorbs infrared light and near infrared light are particularly preferable from the viewpoint of image forming properties. For example, JP-A-58-125246 and JP-A-59-125246.
No. 84356, No. 59-202829, or No. 60
Cyanine dyes described in -78787 and the like,
JP-A-58-173696 and 58-181690
Or methine dyes described in JP-A-58-194595, JP-A-58-112793 and JP-A-58-112793.
Nos. 224793, 59-48187 and 59-7
No. 3996, No. 60-52490, British Patent 434,
875, etc .; the immonium dyes described in U.S. Pat. No. 3,557,012 or JP-A-4-349462;
An aminium dye described in No. 47 is preferably used.
Further, a near-infrared absorbing agent described in US Pat. No. 5,156,938 is also preferably used.

Further, substituted arylbenzo (thio) pyrylium salts described in US Pat. No. 3,881,924 and JP-A-57-142645 (US Pat.
27,169), a trimethinethiapyrylium salt described in
JP-A-58-181051, JP-A-58-220143
Pyrylium compounds described in JP-A-59-216146, JP-A-59-84248, JP-A-59-84249, JP-A-59-146063, and JP-A-59-146061; Cyanine dyes described in the official gazette, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and JP-B 5-135.
The pyrylium compounds described in JP-A Nos. 14 and 5-19702 are particularly preferably used. Another particularly preferred example is a near-infrared absorbing agent described as formulas (I) and (II) in US Pat. No. 4,756,993.

Preferred ionic dyes having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule include the following IR-1 to IR-36, but the present invention is not limited thereto.

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In the present invention, these ionic dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.5 to 50% by weight based on the total solid content of the image forming material. It can be added in a proportion of 15% by weight. If the addition amount is less than 0.01% by weight, an image cannot be formed by this image forming material. If the addition amount exceeds 50% by weight, non-images will be produced when used as a photosensitive layer of a lithographic printing plate precursor. There is a possibility that the portion may become dirty.

To the image forming material of the present invention, other pigments or dyes having an infrared absorbing property can be added for the purpose of improving image forming properties. Examples of pigments 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),
Pigments described in "Printing Ink Technology" published by CMC, 1984) can be used.

The pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments,
Quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dye lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. Methods of surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo)
"Printing ink technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferred in terms of stability in a photosensitive layer coating solution, and when it exceeds 10 μm, it is not preferred 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. Dispersers include ultrasonic dispersers, sand mills, attritors, pearl mills, super mills,
Examples include a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, see “Latest Pigment Application Technology”
(CMC Publishing, 1986).

These dyes or pigments may be added to the image-forming material and added to the image-forming layer together with other components. Alternatively, in preparing a lithographic printing plate precursor, another layer other than the image-forming layer may be provided. You may add there. One of these dyes or pigments may be added, or two or more of them may be mixed for convenience.

[(B) Alkaline aqueous solution soluble resin]
(B) Alkaline aqueous solution soluble polymer compound to be used
The substance is, as follows, in the main chain or side chain of the polymer compound.
It refers to those having an acid group structure. Phenolic hydroxyl group (-
Ar-OH), carboxylic acid group (-CO_TwoH), sulfone
Acid group (-SO_ThreeH), phosphate group (-OPO_ThreeH), Sur
Honamide group (-SO _TwoNH-R), substituted sulfonamido
Acid group (active imide group) (-SO_TwoNHCOR, -S
O_TwoNHSO_TwoR, -CONHSO_TwoR). Where A
r represents a divalent aryl group which may have a substituent;
R has a hydrocarbon group which may have a substituent
You. Among them, preferred acid groups include (b-1) pheno
Hydroxyl group, (b-2) sulfonamide group, (b-
3) An active imide group, particularly (b-1) phenol
Alkaline aqueous solution soluble resin having a hydroxyl group
It is referred to as "a resin having a phenolic hydroxyl group". ) Is the most
It can be preferably used.

(B-1) Examples of the high molecular compound having a phenolic hydroxyl group include polycondensates of phenol and formaldehyde (hereinafter, referred to as "phenol formaldehyde resin") and degeneracy 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) and a novolak resin such as a condensation polymer of formaldehyde, 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. As the monomer having a phenol group to be used,
Examples 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, 2- (4-hydroxyphenyl) ethyl acrylate, 2- (2-hydroxyphenyl) ethyl meth Relate, 2- (3-hydroxyphenyl) ethyl methacrylate can be suitably used 2- (4-hydroxyphenyl) ethyl methacrylate. The weight average molecular weight of the polymer is 5.0 × 10
^{2 to} 2.0 × 10 ⁴ and a number average molecular weight of 2.0 × 10 ²
Those having a size of from 1.0 to 10 ⁴ are preferable in view of image forming properties. Moreover, not only these resins are used alone, but also
A combination of more than two types may be used. When used in combination, a C3-C8 polymer 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. These resins having a phenolic hydroxyl group have a weight average molecular weight of 500 to 20.
Those having a number average molecular weight of 200 to 10000 at 000 are preferred.

In the case of (b-2) an alkaline water-soluble polymer compound having a sulfonamide group, the main monomer constituting the polymer compound is homopolymerized with (a-2) a polymerizable monomer having a sulfonamide group, Alternatively, a polymer compound obtained by copolymerizing the monomer with another polymerizable monomer can be used. Examples of the polymerizable monomer having a sulfonamide group include, in one molecule, at least one sulfonamide group —NH—SO ₂ — having at least one hydrogen atom bonded to a nitrogen atom, and at least one polymerizable unsaturated bond. And a monomer comprising a low-molecular compound having the same. 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 (3) to (7).

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Where X¹, X^TwoIs -O- or-
NR¹⁷Indicates-. R^{twenty one}, R^{twenty four}Is a hydrogen atom or-
CH_ThreeRepresents R^{twenty two}, R^{twenty five}, R²⁹, R³², R³⁶Each
Alkylene having 1 to 12 carbon atoms which may have a substituent
Group, cycloalkylene group, arylene group or aralkyl
Represents a len group. R^{twenty three}, R²⁷, R³³Are hydrogen atoms, respectively
C1-C12 alkyl which may have a substituent
Group, cycloalkyl group, aryl group or aralkyl group
Show. Also, R²⁶, R²⁷Has a substituent
C1-C12 alkyl group, cycloalkyl
Group, an aryl group, and an aralkyl group. R²⁸, R³⁰, R
³⁴Is a hydrogen atom or -CH_ThreeRepresents R³¹, R³⁵Each
1 to 12 carbon atoms which may have a single bond or a substituent
Alkylene group, cycloalkylene group, arylene group or
Represents an aralkylene group. Y¹, Y ^TwoIs a single bond
Or -CO-.

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

(B-3) In the case of an alkali water-soluble polymer compound having an active imide group, the compound has an active imide group represented by the following formula in the molecule, and is a main monomer constituting the polymer compound. (B-3) As a monomer having an active imide group, a monomer comprising a low-molecular compound having an active imino group represented by the following formula and one or more polymerizable unsaturated bonds in one molecule. And a polymer compound obtained by copolymerizing the above.

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

In the alkaline water-soluble copolymer which can be used in the present invention, the monomers containing the acidic groups (b-1) to (b-3) need not be one kind but have the same acidic group. Those obtained by copolymerizing two or more monomers or two or more monomers having different acidic groups 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)
To (b-3) preferably contains at least 10 mol% of a monomer having an acidic group as a copolymer component.
Those containing at least mol% are more preferred. 10 copolymer components
If the amount is less than mol%, the interaction with the resin having a phenolic hydroxyl group becomes insufficient, and the effect of improving the development latitude, which is an advantage of using a copolymer component, becomes insufficient.

The copolymer (b-1)
To (b-3) other than the monomer containing an acidic group. As examples of the monomer that can be used as the copolymer component, the following monomers (1) to (12) can be used.

[0100]

(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, 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 water-soluble polymer compound, those having a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more, irrespective of a homopolymer or a copolymer, are preferable in view of film strength. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the degree of dispersion (weight average molecular weight / number average molecular weight) is 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.

These alkaline water-soluble polymer compounds include:
One type or a combination of two or more types may be used, and the total solid content of the image forming material is 30 to 99% by weight, preferably 40 to 95% by weight, particularly preferably 50% by weight.
It is used in an amount of up to 90% by weight. When the amount of the alkali-soluble polymer compound is less than 30% by weight, the durability of the recording layer is deteriorated.
It is not preferable in terms of durability.

[(C) Compound that Generates Acid by Heat] In the present invention, the compound that generates an acid by heat (hereinafter, appropriately referred to as an acid generator) is decomposed by heating at 100 ° C. or more to generate an acid. Refers to a compound that The generated acid is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. Examples of the acid generator suitably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. More specifically, US Pat.
-20629. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable. As diazonium salts, US Pat. No. 3,867,
No. 147, U.S. Pat. No. 2,6
The diazonium compounds described in JP-A-32,703 and the diazo resins described in JP-A-1-102456 and JP-A-1-102457 are also preferable. Also,
Benzyl sulfonates described in US 5,135,838 and US 5,200,544 are also preferred.
Further, JP-A Nos. 2-100054 and 2-100
Active sulfonic acid esters and disulfonyl compounds described in Japanese Patent Application No. 055 and Japanese Patent Application No. 8-9444 are also preferable. Besides, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable.

These acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 4% by weight, based on the total solid content of the image forming material.
0% by weight, more preferably 0.5 to 30% by weight, is added to the image forming material. 0.01% by weight
If it is less than, an image cannot be obtained. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing.

These compounds may be used alone.
Also, two or more kinds may be used in combination. Since the acid generators listed here can be decomposed by irradiation with ultraviolet rays, the image forming material of the present invention can record images not only with infrared rays but also with ultraviolet rays.

[(D) Crosslinking Agent Cross-Linked by Acid] A cross-linking agent cross-linked by an acid (hereinafter referred to as “d)
(Referred to as “acid crosslinking agent” or simply “crosslinking agent” as appropriate). 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 aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group, an acetoxymethyl group or an alkoxymethyl group. Is mentioned. 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, compounds having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group are preferred. 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 formulas (8) to (11).

[0111]

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[0112]

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In the above formulas, L _{1 to} L ₈ each independently represent a group having 18 carbon atoms such as methoxymethyl and ethoxymethyl.
The following shows a hydroxymethyl group or an alkoxymethyl group substituted with an alkoxy group. 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) As the compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, 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. More preferred examples include, for example, at least two free N-hydroxymethyl groups,
A melamine-formaldehyde derivative having an N-alkoxymethyl group or an N-acyloxymethyl group is exemplified, and among them, an N-alkoxymethyl derivative is 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 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 1,539,192.

The crosslinking agents (i) to (iii) which can be used in the present invention are from 5 to 80% by weight, preferably from 10 to 75% by weight, particularly preferably from 10 to 75% by weight, based on the total solids of the image forming material. It is in the range of 20-70% by weight. If the added amount of the crosslinking agent is less than 5% by weight, the durability of the photosensitive layer of the obtained image forming material is deteriorated, and 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 (12) as a crosslinking agent.

[0118]

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In the above general formula (5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred substituents 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. Because of high sensitivity, Ar ¹ includes an unsubstituted benzene ring and a naphthalene ring, or a halogen atom, a hydrocarbon group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, A benzene ring and a naphthalene ring having as substituents an alkylthio group, a nitro group or the like of several or less are particularly preferred.

R¹And R^TwoAre the same but different
Hydrogen atom or carbon with 12 or less carbon atoms
Shows a hydride group. Because of the ease of synthesis, R
¹And R^TwoIs a hydrogen atom or a methyl group
Particularly preferred. R^ThreeIs a hydrogen atom or 12 or more carbon atoms
Shows the lower hydrocarbon group. Because of the high sensitivity, R ^Three
Represents, for example, a methyl group, an ethyl group, a propyl group,
Hydrocarbon groups having 7 or less carbon atoms, such as xyl and benzyl groups
Is particularly preferred. m represents an integer of 2 to 4
You. n shows the integer of 1-3.

Specific examples of the phenol derivative represented by the general formula (12) preferably used in the present invention are shown below (crosslinking agents [KZ-1] to [KZ-8]). It is not limited to.

[0122]

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[0123]

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

[0125]

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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 form 2,4,6-trihydroxymethylphenol, and subsequently reacting with ethanol in the presence of an acid such as sulfuric acid. Thus, the compound can also be synthesized by a route represented by the following [Reaction formula 2]. Reaction formula [2]

[0127]

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These phenol derivatives may be used alone or in combination of two or more. Further, when synthesizing these phenol derivatives, the phenol derivatives may be condensed with each other to produce by-products such as dimers and trimers, but these impurities may be used while containing these impurities. , Even in this case, the impurity is 3
It is preferably at most 0%, more preferably at most 20%.

In the present invention, the phenol derivative accounts for 5 to 70% by weight, preferably 10% by weight, based on the total solid content of the image forming material.
It is used at an addition amount of ５０50% by weight. Here, if the addition weight of the phenol derivative as a cross-linking agent is less than 5% by weight, the film strength of the image area at the time of image recording deteriorates, and
Exceeding 0% by weight is not preferred in terms of stability during storage.

[Other Components] The image-forming material of the present invention may further contain various additives, if necessary. For example, onium salts, aromatic sulfone compounds,
An aromatic sulfonic acid ester compound or the like acts as a thermally decomposable substance, and therefore, it is preferable to add such a substance because dissolution inhibition of an image area in a developer can be improved.

Examples of the onium salt include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. Suitable onium salts for use in the present invention include, for example, S.I. I. Sch1e
singer, Photogr. Sci. Eng. , 1
8, 387 (1974); S. Ba1eta1, P
oylmer, 21, 423 (1980) or diazonium salts described in JP-A-5-158230;
U.S. Pat. Nos. 4,069,055 and 4,069,05
No. 6, or ammonium salt described in JP-A-3-140140; C. Neckereta1, Mac
Romelecu1es, 17.2468 (198
4), C.I. S. Weneta1, Teh, Proc. C
onf. Rad. CuringASIA, p478To
kyo, Oct (1988); U.S. Pat. No. 4,069,
A phosphonium salt described in J. 055 or 4,069,056; V. Clive11oeta1, Ma
cromorecu1es, 10 (6), 1307 (1
977), Chem. & Eng. News. Nov. 2
8, p31 (1988), EP 104,143.
Nos. 339,049 and 410,201.
JP-A-2-150848 or JP-A-2-150848
JP-A-296514, an iodonium salt described therein, J. Am. V.
Clive11oeta1, Po1ymerJ. 17,
73 (1985); V. Clive11oeta
1. J. Org. Chem. , 43.3055 (197
8); R. Watteta 1, J.M. Po1ymer
Sci. , PolymerChem. Ed. , 22.1
789 (1984); V. Clive11oeta
1, PolymerBu11. , 14,279 (198
5). V. Clive11oeta1, Macro
morecu 1es, 14 (5), 1141 (198
1). V. Clive 11 eta1, J.I. Po1
ymer Sci. , PolymerChem. E
d. , 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,
339,049, 4,760,013, 4,
Nos. 7,34,444 and 2,833,827, German Patent Nos. 2,93804,626 and 3,604,580
Or the sulfonium salt described in JP-A-3,604,581; V. Clive11oeta1, Macro
morecu1es. 10 (6), 1307 (197
7); V. Clive 11 eta1, J.I.
Po1ymerSci. , Po1ymerChemic
h. , 17.1047 (1979), selenonium salts described in C.I. S. Weneta1, Teh, Proc. C
onf. Rad. CuringASIA, P478To
kyo, Oct (1988).

The counter ions of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl -Benzenesulfonic acid and paratoluenesulfonic acid. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

The weight of the onium salt additive is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight. In the present invention, the additive and the binder are preferably contained in the same layer.

For the purpose of further improving sensitivity, cyclic acid anhydrides, phenols and organic acids can be used in combination. As the cyclic acid anhydride, US Pat. No. 4,115,
No. 128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,
6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride,
Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone,
4 ', 4 "-trihydroxytriphenylmethane, 4,
4 ', 3 ", 4"-tetrahydroxy-3,5,3',
5'-tetramethyltriphenylmethane and the like. Further, as the organic acids, JP-A-60-88942
Sulfonic acids, sulfinic acids, alkyl sulfates, and the like described in JP-A-2-96755 and JP-A-2-96755.
Examples include phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid,
Ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene -1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. The proportion of the cyclic acid anhydride, phenols and organic acids in the image forming material is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight,
Particularly preferably, it is 0.1 to 10% by weight.

Further, in the image forming 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, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. Specific examples of the surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example,
Trade name “Amogen K”: manufactured by Dai-ichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the image forming material is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

In the image forming material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes and pigments as image colorants can be added.
Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. In particular,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-36223, 54-74728, 6
No. 0-3626, No. 61-143748, No. 61-1
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-51644 and JP-A-63-58440 can be exemplified. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. 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 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-2932
The dyes described in JP-B-47 are particularly preferred. These dyes are used in an amount of 0.01 to 1 based on the total solid content of the image forming material.
0% by weight, preferably 0.1 to 3% by weight can be added to the image forming material. Further, a plasticizer is added to the image forming material of the present invention, if necessary, in order to impart flexibility and the like to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers are used.

Further, in addition to these, epoxy compounds, vinyl ethers, and JP-A-8-27655
Patent Document 8 discloses a phenol compound having a hydroxymethyl group, a phenol compound having an alkoxymethyl group and Japanese Patent Application No. 9-32837 filed by the present inventors.
The dissolution suppression enhancing cross-linking agent described in the specification can be appropriately added according to the purpose.

The lithographic printing plate precursor can be prepared by dissolving a coating solution for a photosensitive layer containing the image forming material of the present invention or a coating solution component for a desired layer such as a protective layer in a solvent and coating the solution on a suitable support. Can be manufactured. 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-butyrolactone, toluene,
Water and the like can be mentioned, but it is 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 coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but generally 0.5 to 5.0 g / m ² is preferred for a photosensitive printing plate. As a method of applying, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive layer deteriorate.

In the photosensitive layer coating solution using the photosensitive composition of the present invention, a surfactant for improving coating properties,
For example, a fluorine-based surfactant as described in JP-A-62-170950 can be added.
The preferred addition amount is 0.01 to 1% by weight of the total printing plate material.
More preferably, it is 0.05 to 0.5% by weight.

The support used in the lithographic printing plate precursor according to the present invention is a dimensionally stable plate-like material.
Paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, butyric acid) Cellulose, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), a metal-laminated or vapor-deposited paper as described above,
Alternatively, a plastic film or the like is included.

As the support used in the lithographic printing plate precursor of the present invention, a polyester film or an aluminum plate is preferable. Among them, an aluminum plate having good dimensional stability and relatively low cost 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 foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is approximately 0.1 mm to 0.6 mm, preferably 0.15 m.
m to 0.4 mm, particularly preferably 0.2 mm to 0.3 m
m.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, 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, if necessary, and then subjected to an anodic oxidation treatment, if desired, in order 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 vary depending on the electrolyte to be used, and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat. Nos. 2,7,7
No. 14,066, No. 3,181,461, No. 3,2
There is an alkali metal silicate (e.g., sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 80,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,46.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in JP-A Nos. 1 and 4,689,272 is used.

The lithographic printing plate precursor according to the invention is provided with a positive or negative photosensitive layer containing the image forming material according to the invention on a support. Can be provided. Various organic compounds are used as the undercoat layer component, for example, carboxymethyl cellulose,
Dextrin, gum arabic, phosphonic acids having an amino group such as 21 aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, naphthylphosphonic acid,
Organic phosphonic acids such as alkyl phosphonic acid, glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, phenylphosphoric acid which may have a substituent, naphthyl phosphoric acid, organic phosphoric acid such as alkyl phosphoric acid and glycerophosphoric acid, Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, amino acids such as glycine and β-alanine, and hydroxy groups such as triethanolamine hydrochloride Or a mixture of two or more of them.

The organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is used. A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent or a mixed solvent thereof to adsorb the above compound by immersing the aluminum plate, and then washed and dried with water or the like to provide an organic undercoat layer. . In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C, preferably 25%.
To 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The pH of the solution used for this is adjusted to pH 1 to 12 by a basic substance such as ammonia, triethylamine, potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be adjusted to the range. Further, a yellow dye may be added for improving the tone reproducibility of the image forming material. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

The lithographic printing plate precursor prepared as described above is usually subjected to image exposure and development processing. Examples of the light source of the actinic ray used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. Also g
Lines, i-lines, Deep-UV light, high density energy beams (laser beams) are also used. Laser beams include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, K
An rF excimer laser, a solid-state laser, a semiconductor laser and the like are mentioned. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the lithographic printing plate precursor according to the invention, conventionally known alkaline aqueous 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 And inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is silicon oxide SiO ₂ and alkali metal oxides are components of the silicate
This is because developability can be adjusted by the ratio and concentration of M ₂ O. For example, JP-A-54-62004 discloses
The alkali metal silicate described in JP-B-57-7427 is effectively used.

Further, in the case of developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. To the developing solution and the replenishing solution, various surfactants and organic solvents can be added as necessary 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 bisulfite, and an organic carboxylic acid, an antifoaming agent, and a water softener. Can be added. The 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 forming material of the present invention is used as a printing plate, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the 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 photosensitive lithographic printing plate precursor using the image forming material of the present invention will be described. If the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has unnecessary image portions (for example, film edge marks of the original film), unnecessary portions are unnecessary. Erasing of the image portion is performed. Such erasing is preferably performed by applying an erasing liquid as described in, for example, Japanese Patent Publication No. 2-129393 to an unnecessary image portion, leaving the same for a predetermined period of time, and then rinsing with water. A method described in JP-A-59-174842, in which active light guided by an optical fiber is applied to an unnecessary image portion and then developed, can be used.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired. Is subjected to a burning process. When the lithographic printing plate is subjected to a burning process, before the burning process, Japanese Patent Publication Nos. 61-2518 and 55-28062,
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 62-31859 and 61-159655. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, 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.

The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m ² (dry weight) is appropriate. The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-130").
0 "). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0156]

EXAMPLES The present invention will be described below with reference to synthesis examples and examples of alkaline infrared absorbers, but the scope of the present invention is not limited to these synthesis examples and examples.

[0157]

The synthesis of the infrared absorbing skeleton useful in the present invention is as follows:
As shown in the following scheme, the reaction 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)
It can be carried out according to the method for synthesizing oxonol dyes described on pages 74 to 289.

[0159]

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Examples of the methylene chain donor include the following structures.

[0161]

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(Synthesis Example 1: Synthesis of Compound A-1) Q-1
(0.1 mol), Q-2 (0.05 mol), and methanol (500 ml) were placed in a beaker, and triethylamine (0.2 mol) was added dropwise over 10 minutes. It became a suspension. Tetrabutylammonium bromide (0.2 mol) was added to the solution, and the mixture was stirred for 30 minutes to precipitate a dark blue solid. The precipitated solid was collected by filtration and washed with water to obtain A-1 in a yield of 55%. The structure of A-1 is represented by mass spectrometry, 1H-NM
R, which was confirmed by infrared absorption spectrum.
1 shows a synthesis scheme.

[0163]

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(Synthesis Example 2: Synthesis of IR-23) A-1
(0.05 mol) and A-2 (0.05 mol) were mixed in 100 ml of methanol. The solid was collected by filtration and washed well with methanol. This solid and A-2 were mixed again in methanol to obtain IR-23 at a yield of 60%. The synthesis scheme of compound IR-23 is shown below.

[0165]

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By the salt exchange, IR-22 and IR-24 were similarly synthesized by the above-mentioned synthetic route.

(Synthesis Example 3: Synthesis of Compound A-3) Q-1
(0.1 mol), Q-3 (0.05 mol) and methanol (500 ml) were placed in a beaker, and triethylamine (0.2 mol) was added. After stirring at room temperature for 10 hours, tetrabutylammonium bromide (0.2 mol
1) was added. The precipitated solid was collected by filtration and separated by column chromatography to obtain A-3 (yield: 15%). The synthesis scheme of Compound A-3 is shown below.

[0168]

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The compound A-3 was subjected to salt exchange to obtain IR-9, IR-12 and IR-33.

-Evaluation as Positive Image Forming Material- (Examples 1 to 8) [Preparation of Substrate] 0.3 mm thick aluminum plate (material
1050) was degreased by washing with trichloroethylene.
After, nylon brush and 400 mesh pumice-water suspension
The surface was grained using a liquid and washed well with water. This
Plate for 9 seconds in a 25% aqueous solution of sodium hydroxide at 45 ° C
Etching by immersion, washing with water, and then 20% nitric acid
For 20 seconds and washed with water. At this time,
Etching amount is about 3g / m ^TwoMet. Next, this plate
% Sulfuric acid as electrolyte and current density 15A / dm^Two3g /
m^TwoAfter providing a direct current anodic oxide coating of
Furthermore, the following undercoat liquid is applied, and the coating film is dried at 90 ° C. for 1 minute.
Dried. The coating amount of the dried coating film is 10 mg / m^TwoSo
Was.

<Composition of Undercoat Liquid> 0.5 g of β-alanine 95 g of methanol 5 g of water

The following substrate was prepared by changing the infrared absorbing agent in the following photosensitive solution 1 as shown in Table 1 below, and each was applied so that the coating amount became 1.8 g / m ^2. 1 to 8 planographic printing plate precursors were obtained.

<Composition of Photosensitive Solution 1> m, p-cresol novolak (m / p ratio: 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) 1.0 g * soluble in alkaline water High molecular compound ・ Infrared absorber described in Table 1 0.2 g * (Ionic dye according to the present invention) ・ Dye in which the counter anion of Victoria Pure Blue BOH is changed to 11-naphthalene sulfonic acid anion 0.02 g ・ Fluorine-based interface Activator (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g • γ-butyrolactone 3 g • Methyl ethyl ketone 8 g • 1-methoxy-2-propanol 7 g

(Examples 9 to 16) [Synthesis of Copolymer as Alkaline Aqueous Solution-Soluble Polymer Compound] <Synthesis Example (Copolymer 1)> Methacryl was placed in a 500-ml three-necked flask equipped with a stirrer, a condenser, and a dropping funnel. Acid 3
1.0 g (0.36 mol), ethyl chloroformate 39.1
g (0.36 mol) and 200 ml of acetonitrile were added, and the mixture was stirred while cooling in an ice-water bath. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped by a dropping funnel over about 1 hour. After dropping,
The ice water bath was removed and the mixture was stirred at room temperature for 30 minutes.

To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, which was then washed with 500 m of water.
Then, the slurry was filtered and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
210 mol), and 2.05 g (0.05 g) of ethyl methacrylate.
180 mol), 1.11 g of acrylonitrile (0.02
1 mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. This mixture was mixed with “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.).
0.15 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. N- (p-
Aminosulfonylphenyl) methacrylamide 5.04
g, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of "V-65" were added dropwise over 2 hours using a dropping funnel. After the addition was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, methanol 40
g was added to the mixture, and the mixture was cooled. The obtained mixture was poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. I got The weight average molecular weight of this copolymer 1 (polystyrene standard) was measured by gel permeation chromatography and found to be 53,000.
It was 0.

Same as the substrate used in Examples 1 to 6
Next, in the following photosensitive solution 2, an infrared absorber was used as shown in Table 2 below.
Were prepared as described above, and the coating amount of each was 1.8.
g / m ^TwoAnd lithographic printing of Examples 9-16
The original plate was obtained. <Composition of Photosensitive Liquid 2> <Composition of Photosensitive Liquid 1> ・ 11.0 g of the above copolymer ※ Alkaline water soluble polymer compound ・ Infrared absorbent 0.1 g of Table 2 ※ (ionic dye according to the present invention) p-Toluenesulfonic acid 0.002 g ・ Dye in which the counter anion of Victoria Pure Blue BOH is converted to an 11-naphthalenesulfonic acid anion 0.02 g ・ Fluorinated surfactant (MegaFac F-177, Dainippon Ink and Chemicals, Inc.) 0.05 g ・ γ-butyrolactone 8 g ・ Methyl ethyl ketone 8 g ・ 1-methoxy-2-propanol 4 g

(Comparative Examples 1 to 3) In Example 1, except that the ionic dye compounded in the photosensitive solution 1 was replaced with infrared absorbents B-1, B-2 and A-2 represented by the following structure, The lithographic printing plate precursors of Comparative Examples 1 to 3 were obtained in exactly the same manner as in Example 1.

[0179]

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(Comparative Example 4) In Example 1, the photosensitive liquid 1
The ionic dye blended with the infrared absorbent A-1 was added at 0.1.
A lithographic printing plate precursor of Comparative Example 4 was obtained in exactly the same manner as in Example 1 except that 05 g and A-2 were replaced with 0.05 g.

Comparative Examples 5 to 7 In Example 7, except that the ionic dye compounded in the photosensitive solution 2 was replaced with the infrared absorbents B-1, B-2 and A-2 shown in the above structure. The lithographic printing plate precursors of Comparative Examples 5 to 7 were obtained in exactly the same manner as in Example 7.

(Comparative Example 8) In Example 7, the photosensitive solution 2
The ionic dye blended with the infrared absorbent A-1 was added at 0.1.
A lithographic printing plate precursor of Comparative Example 4 was obtained in exactly the same manner as in Example 7, except that 05 g and A-2 were changed to 0.05 g.

[Evaluation of Performance of Lithographic Printing Plate Precursor] Performance of the lithographic printing plate precursors of Examples 1 to 12 and Comparative Examples 1 to 8 produced as described above was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2.

(Evaluation of Image Formability: Sensitivity and Development Latitude) The obtained lithographic printing plate precursor was exposed using a semiconductor laser having a wavelength of 840 nm and a YAG laser having a wavelength of 1064 nm, and then developed by Fuji Photo Film Co., Ltd. DP-
4. An automatic processor equipped with a rinse liquid FR-3 (1: 7) (manufactured by Fuji Photo Film Co., Ltd.): "PS Processor 9
00VR "). At this time, DP-4 was used at two levels, one diluted 1: 6 and one diluted 1:12, and the line width of the non-image portion obtained with each developer was measured. The irradiation energy of the laser corresponding to was obtained, and this was used as the sensitivity. The difference between the standard 1: 6 dilution and 1:12 dilution was recorded. 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 obtained lithographic printing plate precursor was stored under high-temperature and high-humidity conditions at a temperature of 45 ° C. and a humidity of 75% for 3 days before laser exposure. And the sensitivity was measured in the same manner and compared with the above results. If the variation in sensitivity is 20 mJ / cm ² or less, the storage stability is good and is at a practical level.

[0186]

[Table 1]

[0187]

[Table 2]

From the results shown in Tables 1 and 2, Examples 1 to 16 were obtained.
It was found that all of the lithographic printing plate precursors of Comparative Examples 1 to 8 had higher sensitivity to the infrared laser than the lithographic printing plate precursors of Comparative Examples 1 to 8. In addition, the difference in sensitivity between the two dilution concentrations of the developer is extremely small, and 20 mJ /
has achieved cm ² or less performance, it was confirmed to have excellent development latitude. Furthermore, from the results of the evaluation of storage stability, all of the lithographic printing plate precursors of the present invention require a fluctuation of sensitivity before and after storage of 20 mJ, which is practically required.
/ Cm ² or less.

-Evaluation as negative image forming material- (Examples 17 to 24) [Preparation of lithographic printing plate] Solution [A]-Thermal acid generator X-1 (the following structural formula) 0.15 g-Table 3 0.10 g * (ionic dye according to the present invention) ・ Novolak resin obtained from phenol and formaldehyde (weight average molecular weight 10,000) 1.5 g ・ Crosslinking agent MM-1 (the following structural formula) 0.50 g ・Fluorosurfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.03 g ・ Methylethylketone 15 g ・ 1-Methoxy-2-propanol 10 g ・ Fluorosurfactant 0.03 g (Mega FAK F-177, Dainippon Ink & Chemicals, Methyl alcohol 5 g

[0190]

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In the solution [A] having the above composition, the type of the ionic dye of the present invention was changed to that shown in Table 3, and
Different solutions were prepared. Each of the solutions was applied to the above support, and dried at 100 ° C. for 1 minute to obtain a negative type lithographic printing plate. The coating weight after drying was 1.3 g / m ² .

The obtained negative type lithographic printing plate material (Example 1)
7 to 24) were exposed with a semiconductor laser emitting infrared light having a wavelength of 830 nm and a YAG laser emitting infrared light having a wavelength of 1064 nm. After exposure, a heat treatment was performed for 1 minute in an oven at 140 ° C., and a developing solution manufactured by Fuji Photo Film Co., Ltd.
Processing was carried out through an automatic processor equipped with P-4 (1: 8) and a rinsing liquid FR-3 (1: 7). In each case, good negative images were obtained. Further, the negative type lithographic printing plate material was stored for 3 days under a high-temperature and high-humidity condition of a temperature of 45 ° C. and a humidity of 75%, exposed to laser in the same manner as described above, heated, and developed. Even after such a durability test, good negative images were obtained.

(Comparative Examples 9 to 11) In the solution [A] used in Examples 17 to 24, the ionic dye according to the present invention was replaced with the infrared absorbents B-1, B-2, A
Except for using -2, lithographic printing plate precursors of Comparative Examples 9 to 11 were obtained in exactly the same manner as in Example 17.

(Comparative Example 12) In the solution [A] used in Examples 17 to 24, 0.05 g of the ionic dye of the present invention, 0.05 g of the infrared absorbent A-1 and 0.
A lithographic printing plate precursor of Comparative Example 2 was obtained in exactly the same manner as in Example 17 except that the amount was changed to 05 g.

[0195]

[Table 3]

The resulting planographic printing plate material (Comparative Examples 9-1)
2) was exposed to a semiconductor laser without performing a durability test in the same manner as in Examples 17 to 24, and after heat treatment and development, favorable negative images were obtained in all cases. After storage for 3 days under a high temperature and humidity condition of 45 ° C. and 75% humidity as in Examples 17 to 24, exposure to a semiconductor laser and evaluation were carried out. As is clear from Tables 1 to 3, according to the comparison between Examples 1 to 24 and Comparative Examples 1 to 12, the lithographic printing plate material using the image forming material of the present invention shows that the negative type and the positive type are both infrared rays. It was found that the film had high sensitivity to laser, had a good development latitude, and had excellent image forming properties. Further, there was little change in sensitivity before and after storage under high temperature and high humidity conditions, and the storage stability was excellent.

[0197]

According to the present invention, it is possible to provide an image-forming material having high sensitivity and excellent stability in sensitivity to the concentration of a developer, that is, excellent development latitude and storage stability. In addition, a lithographic printing plate precursor using this image forming material can be directly made by infrared laser, and has high sensitivity,
In addition, there is an excellent effect that the developing latitude and the storage stability are good.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 2H025 AA00 AA01 AA04 AB03 AC08 AD01 AD03 BE00 CB52 CC13 CC17 FA10 FA17 2H096 AA06 BA06 BA11 EA04 EA23 GA09 2H114 AA04 BA02 BA05

Claims (4)

[Claims] 1. An infrared laser-sensitive image-forming material comprising, in one molecule, an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton. 2. An infrared laser-sensitive image forming material comprising: (a) and (b): (A) an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule; and (b) a polymer compound which is insoluble in water and soluble in an aqueous alkali solution. 3. An infrared laser-sensitive image-forming material comprising (a) to (d) below. (A) an ionic dye having a cationic infrared absorbing skeleton and an anionic infrared absorbing skeleton in one molecule, (b) a polymer compound insoluble in water and soluble in an aqueous alkali solution, and (c) heat Compounds that generate an acid, and (d) compounds that crosslink using an acid as a catalyst. 4. A lithographic printing plate precursor comprising an image forming layer comprising the image forming material according to claim 1 provided on a support.