JPH11119418A - Positive photosensitive composition for infrared laser beams - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition wide in development latitude and capable of forming a printing plate directly from digital information and suitable for forming a lithographic printing plate by incorporating an alkali- soluble polymer compound and a substance absorbing light and generating heat and a specified disulfonyl or sulfonyl compound. SOLUTION: The photosensitive composition contains the alkalisoluble polymer compound and the substance absorbing light and generating heat and the compound represented by formula I: R<1> -SO2 -SO2 -R<2> or formula II: R<1> -SO2 -R<2> . In the formulae I and II, each of R<1> and R<2> is an optionally substituted alkyl or alkenyl or aryl group. When the material containing such a composition is irradiated with laser beams, the exposed parts absorb the light and generate heat to reduce interaction between the compound of the formula I or formula II and the alkali-soluble compound and to increase alkali solubility, thus permitting the difference of the solubilities in an alkaline developing solution between the exposed parts and the unexposed parts to be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a positive photosensitive lithographic printing plate for infrared laser which can be used as an offset printing master, and more particularly to a positive photosensitive lithographic printing plate for so-called direct plate making which can make a plate directly from a digital signal of a computer or the like. The present invention relates to a positive photosensitive composition for an infrared laser suitable for use.

[0003]

2. Description of the Related Art Conventionally, as a system for directly making a plate from digital data of a computer, an electrophotographic method, a photopolymerization system using a combination of exposure by an Ar laser and post-heating, and a silver salt photosensitive material laminated on a photosensitive resin are used. Known examples include a silver master type, a silicon master type, and a method in which a silicone rubber layer is broken by a discharge breakdown or a laser beam. However, those using electrophotography require complicated processes such as charging, exposure, and development, and require a complicated and large-scale apparatus.
In the above method, a post-heating step is required, and a high-sensitivity plate material is required, which makes it difficult to handle in a bright room. In the methods (1) and (2), the use of a silver salt complicates the processing and has the disadvantage of increasing the cost. The other method is a method with a relatively high degree of perfection, but has a problem in removing silicone residue remaining on the plate surface.

On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared have become easily available in high-output and small-sized ones. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like. As a conventional image recording material, Japanese Patent Application Laid-Open No. 7-285275 discloses a binder such as a cresol resin and a substance which generates heat by absorbing light, which is thermally decomposable such as quinonediazide and decomposed. If not, a positive image recording material containing a substance that substantially reduces the solubility of the binder has been proposed. However, when exposed to a laser having a low power, the decomposition rate of the thermally decomposable substance is low, and the developability of a liquid having a low developing ability, that is, the developability under an under condition is insufficient. Accordingly, it is an object of the present invention to provide a photosensitive composition having a wide latitude in development, that is, a composition having a wide latitude.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition having a wide development latitude, in particular, a conventional processing apparatus or a printing apparatus as it is. An object of the present invention is to provide a positive photosensitive composition for an infrared laser suitable for use in a possible positive photosensitive lithographic printing plate.

[0006]

Means for Solving the Problems The inventors of the present invention have studied various compounds that interact with an alkali-soluble polymer compound. And have led to the present invention. That is, the above object, at least, an alkali-soluble polymer compound, a positive photosensitive composition for infrared laser containing a substance that absorbs light and generates heat,
The problem is solved by providing the photosensitive composition, which comprises a compound represented by the following formula.

Embedded image R ¹ —SO ₂ —SO ₂ —R ² (I)

R ¹ -SO ₂ -R ² (II) In the formula, R ¹ and R ² may be the same or different and represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention, as described above, a more specific infrared photosensitive composition conventionally known, namely, an alkali-soluble polymer compound, and more particularly an infrared photosensitive composition containing a substance that absorbs light and generates heat. It is characterized by adding a disulfone compound or a sulfone compound. When a material having such a composition is irradiated with a laser, the exposed portion absorbs light to generate heat, and the heat is generated by the above (I) or (I).
The interaction between the disulfone compound or the sulfone compound represented by I) and the alkali-soluble polymer compound is reduced to increase the alkali solubility. On the other hand, no heat is generated in the unexposed portion, and thus the disulfone compound or the sulfone compound is mixed with the alkali. It is considered that the interaction with the soluble polymer compound, that is, the deterrent to the solubility in the alkali developer is maintained. As a result, it is considered that the difference in solubility between the exposed portion and the unexposed portion in the alkali developing solution is increased, and the development latitude is widened.

The interaction between the sulfone compound represented by the above (II) and a novolak resin which is an alkali-soluble polymer is also described in Proc. SPIE, vol. 1086 , 48 (1989). This document describes only the interaction between the additive (II) having the above structure and the novolak which is an alkali-soluble polymer, and shows that the interaction is reduced by the heat of laser exposure to obtain an image. However, this point is newly found for the first time in the present invention. Conventionally, to the infrared-sensitive composition as described above, a thermally decomposable compound such as an onium salt was added, and in a state where it was not decomposed, the alkali solubility of the alkali-soluble polymer compound was suppressed, while thermal decomposition was performed. In this state, it is known that the inhibitory power is reduced, the alkali solubility is increased, and development is performed by utilizing the difference in alkali solubility.However, the present invention relates to the case where such a known thermally decomposable compound is used. A wider development latitude could be achieved as compared to

The positive photosensitive composition for an infrared laser according to the present invention is an infrared photosensitive composition containing an alkali-soluble polymer compound and a substance which absorbs light and generates heat. It is characterized by including.

Embedded image R ¹ —SO ₂ —SO ₂ —R ² (I)

Embedded image R ¹ —SO ₂ —R ² (II)

In the formula, R ¹ and R ² may be the same or different and represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group. The alkyl groups of the general formulas (I) and (II) are linear, branched or cyclic, and preferably have 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclohexyl group, and the like. . The substituted alkyl group includes a halogen atom such as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aryl group such as a phenyl group, and a phenoxy group. Such as a monochloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a 2-chloroethyl group, a 2-bromoethyl group, and a 2-methoxyethyl group. , 2-ethoxyethyl, phenylmethyl, naphthylmethyl, phenoxymethyl and the like.

The alkenyl group includes, for example, a vinyl group, and the substituted alkenyl group includes those in which a vinyl group is substituted with, for example, an alkyl group such as a methyl group, for example, an aryl group such as a phenyl group. Specifically, 1-methylvinyl group, 2-methylvinyl group, 1,2
-Dimethylvinyl group, 2-phenylvinyl group, 2- (p
-Methylphenyl) vinyl group, 2- (p-methoxyphenyl) vinyl group, 2- (p-chlorophenyl) vinyl group, 2- (o-chlorophenyl) vinyl group and the like.

The aryl group is preferably a monocyclic or bicyclic aryl group such as phenyl, α-naphthyl, β
-Naphthyl group and the like. Examples of the substituted aryl group include, in addition to the above-mentioned aryl groups, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, for example, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, for example, a chlorine atom Such as those substituted by a halogen atom, a nitro group, a phenyl group, a carboxy group, a hydroxy group, an amide group, an imide group, a cyano group, etc., specifically, a 4-chlorophenyl group, a 2-chlorophenyl group, Bromophenyl group, 4-nitrophenyl group, 4-hydroxyphenyl group, 4-phenylphenyl group, 4-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4
-Methoxyphenyl group, 2-methoxyphenyl group, 4-
Ethoxyphenyl group, 2-carboxyphenyl group, 4-
Cyanophenyl group, 4-methyl-1-naphthyl group, 4-
Chloro-1-naphthyl group, 5-nitro-1-naphthyl group, 5-hydroxy-1-naphthyl group, 6-chloro-2
-Naphthyl group, 4-bromo-2-naphthyl group, 5-hydroxy-2-naphthyl group and the like.

The disulfone compound represented by the general formula (I) used in the present invention is a compound represented by the formula: C. "Journal of Organic Chemistry" by Denser, Jr. et al. (GCDenser, Jr et al., "Journal of Organic Ch."
emistry " 31 , 3418-3419 (1966); P. Hilditch, "Journal of the Chemical Society" (TPHilditch, "Journal of the Chemical Society") 93 , 152
4 to 1527 (1908);
Hinsberg, "Berichte der Deutschen Hemisier Geserschaft" (O. Hinsberg, "Berichte d
er Deutschen Chemischen Gesellschaft ") 49 , 25
93-2594 (1916). That is, in a sulfuric acid aqueous solution, a method of synthesizing from a sulfinic acid represented by the general formula (III) using cobalt sulfate, and a method of synthesizing a compound represented by the general formula (I
V) a method of synthesizing from sulfonic acid chloride represented by
Alternatively, a method of reacting a sulfinic acid represented by the general formula (III) with a sulfonic acid chloride represented by the general formula (IV) under basic conditions may be used.

[0014]

Embedded image R ¹ —SO ₂ H (III)

Embedded image R ² —SO ₂ Cl (IV) (wherein R ¹ and R ² represent R ¹ defined by the general formula (I))
It has the same meaning as ¹ and R ^2. )

The general formula (I) used in the present invention will be described below.
Specific examples of the disulfone compound represented by are shown below.

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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On the other hand, the sulfone compound represented by the general formula (II) used in the present invention is generally obtained by oxidizing a corresponding sulfide compound by a conventional method. Specific examples of the sulfone compound represented by the general formula (II) used in the present invention are described below.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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Examples of the alkali-soluble resin used in the present invention include resins having an acid group such as a phenolic hydroxyl group and a carboxy group. Examples of the resin having a phenolic hydroxyl group include a resole type phenol resin and a novolak type phenol resin. Among them, the novolak resin is preferable. Novolak resins that can be suitably used in the present invention include, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-
Cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-,
o- and m- / p-, m- / o- and o- / p-mixtures), and cresol formaldehyde resins such as mixed formaldehyde resins. Resol type phenolic resins are also preferably used, and phenol /
Cresol (m-, p-, o- and m- / p-, m- /
o- or o- / p-mixtures). Mixed formaldehyde resins are preferred.
Phenol resins described in JP-A-4 are preferred.

Other polymer compounds used in the present invention as alkali-soluble polymer compounds include, for example, copolymers containing a carboxy group. For example,
A copolymer of a monomer having at least one polymerizable unsaturated bond with a carboxy group (COOH group) in one molecule is preferable. Examples of the monomer having a carboxy group include methacrylic acid, acrylic acid, and itaconic acid. In addition, the following general formulas (V) to (VII)
The following monomers are also preferably used.

[0040]

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[0041]

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[0042]

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R ¹ , R ³ , and R ⁵ are hydrogen or a methyl group; R ² , R ⁴ , R ⁶ , and R ⁷ are each an optionally substituted alkylene group having 1 to 12 carbon atoms; Represents a cycloalkylene group, an arylene group, or an aralkylene group,
X is -O- or -NR ⁸ -, Y represents a single bond or -C
Represents an O- group. R ⁸ represents a hydrogen atom, an alkyl group having from 12 to 12 carbon atoms which may have a substituent, a cycloalkyl group, an aryl group, or an aralkyl group. Specifically, N-
(4-carboxyphenyl) -methacrylamide, N-
(2-carboxyphenyl) -acrylamide, N-
(4-chloro-2-carboxyphenyl) -methacrylamide, 4-carboxyphenylethyl methacrylate, 4-carboxystyrene, 2-carboxyphenyloxyethyl acrylate, and the like.

As a monomer for imparting alkali solubility to a polymer compound other than the above-mentioned monomer having a carboxy group, one molecule can be polymerized with a sulfonamide group having at least one hydrogen atom bonded to a nitrogen atom. Monomers consisting of low molecular compounds each having at least one unsaturated bond are preferred. Among them, a monomer composed of a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and an unsubstituted or monosubstituted aminosulfonyl group or a substituted sulfonylamino group is preferable. Examples of such a compound include compounds represented by the following general formulas (VIII) to (XII).

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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In the formula, X ¹ and X ² each represent -O- or-
NR ¹⁷ - represents a. R ¹ and R ⁴ are each a hydrogen atom or-
Represents CH ₃ . R ² , R ⁵ , R ⁸ , R ¹¹ and R ¹⁵ each represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. R ³ , R ¹⁷ and R ¹² represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.
R ⁶ and R ^{16 each} represent an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. R ^7, R ^9, R ¹³ represents a hydrogen atom or -CH _3. R ^10, R ¹⁴ are each a single bond or optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, or aralkylene group. Y ¹ and Y ² each represent a single bond or —CO—.

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

The other monomer other than the above (VIII) to (XII) includes -CO-NH-SO in one molecule.
_A monomer composed of a low-molecular compound having an active imino group represented by _2- and one or more polymerizable unsaturated bonds is also preferable. Specific examples of such a compound include N- (m-aminosulfonyl) methacrylamide,
N- (p-aminosulfonyl) methacrylamide, N-
(P-Toluenesulfonyl) acrylamide and the like can be suitably used. Further, a monomer composed of acrylamide, methacrylamide, acrylate, methacrylate or hydroxystyrene having a phenolic hydroxyl group is also preferably used as another monomer. As such a compound, specifically, N- (4
-Hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, p
-Hydroxyphenyl acrylate, o-, m-, p-
Hydroxystyrene and the like.

As the copolymerization component of the above monomer, for example, the following monomers (1) to (11) can be used, or two or more of the following monomers may be contained. (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 acrylate , Such as alkyl 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-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N Acrylamide or methacrylamide such as -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 and the like.

The weight average molecular weight of these alkali-soluble resins is 500 to 200,000, and the number average molecular weight is 200
Preferably it is ~ 60,000. These alkali-soluble resins may be used alone or in combination of two or more, and are 5 to 99% by weight, preferably 10 to 95% by weight, particularly preferably 20% by weight, based on the total solid content of the image recording material.
It is used in an amount of up to 90% by weight. If the addition amount of the alkali-soluble resin is less than 5% by weight, the durability of the recording layer is deteriorated, and if it exceeds 99% by weight, it is not preferable in terms of both sensitivity and durability.

Other binders used in the present invention include urethane resins. Among them, urethane resins having a carboxy group or a sulfonamide group are preferred. That is, the polyurethane resin suitably used in the present invention comprises a diisocyanate compound and at least one
It is a polyurethane resin having a basic skeleton as a reaction product with a diol compound containing a sulfonamide group to which two H atoms are bonded.

The diisocyanate compound preferably used in the present invention includes 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate,
6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,
Aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethyl Fatty acid diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) alicyclic diisocyanate compounds such as diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; adducts of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate; Of diols and diisocyanates A diisocyanate compound which is a reactant is exemplified.

Examples of diol compounds containing a sulfonamide group having at least one H atom bonded to N include p- (1,1-dihydroxymethylethylcarbonylamino) benzenesulfonamide, p- (1,1 −
N-ethyl form of dihydroxymethylethylcarbonylamino) benzenesulfonamide, N- (m-methylsulfonylaminophenyl) -2,2-dihydroxymethylpropanamide, N- (p-methylsulfonylaminophenyl) -2,2- Dihydroxymethylpropanamide, N- (m-ethylsulfonylaminophenyl)-
2,2-dihydroxymethylpropanamide, N- (p
-Ethylsulfonylaminophenyl) -2,2-dihydroxymethylpropanamide, N- (2,2- (dihydroxyethylaminocarbonyl) ethyl) methanesulfonamide, N- (2,2- (dihydroxyethylaminocarbonyl) ethylbenzenesulfone Amide, N-
(2,2- (dihydroxyethylaminocarbonyl) ethyl-p-toluenesulfonamide and the like.

These diol compounds containing a sulfonamide group can be used alone or in combination of two or more. Further, a diol compound having no sulfonamide group and optionally having another substituent which does not react with isocyanate can be used in combination with a diol compound having a sulfonamide group. Examples of such diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, and 1,6-hexane. Diol, 2-butyl-
1,4-diol, 2,2,4-trimethyl-1,3-
Pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A,
Hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethylsulfone, bis (2-hydroxyethyl) -2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethyl Carbamide), bis (2-hydroxyethyl) -m
-Xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid,
2,2-bis (2-hydroxyethyl) propionic acid,
Examples thereof include 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, and tartaric acid.

The polyurethane resin usable in the present invention is synthesized by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent, adding a known catalyst having an activity corresponding to the respective reactivity, and heating. . The molar ratio of diisocyanate and diol compound used is preferably 0.8: 1 to 1.2: 1, more preferably 0.8: 1.
5: 1.1 to 1.1: 1, and when an isocyanate group remains at the polymer terminal, this terminal is treated with an alcohol, an amine, or the like, so that a polyurethane resin having no isocyanate group finally remaining Are synthesized.

The urethane resin usable in the present invention preferably has a weight average molecular weight of 2,000 or more, more preferably 5,000 to 300,000. The number average molecular weight is 1,
2,000 or more, more preferably 2,000 to 2,
The range is 50,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.
It is in the range of 1-10.

The binder usable in the present invention may contain an unreacted monomer. in this case,
The proportion of the monomer in the binder is desirably 15% by weight or less. The alkali-soluble polymers mentioned above can be used alone, but it is also preferable to mix one or more kinds. Among them, it is preferable to use a mixture of the novolak resin and other binders.

In the present invention, as the substance that absorbs light and generates heat, various pigments or dyes can be used. 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” (CM
C Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984) can be used.

The types of 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).

As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment absorbing infrared light or near infrared light, carbon black is preferably used. Dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246 and JP-A-59-125246.
-84356, JP-A-59-202829, JP-A-60-78787 and the like.
JP-A-58-173696, JP-A-58-18169
0, methine dyes described in JP-A-58-194595, JP-A-58-112793, and JP-A-58-112793.
Naphthoquinone dyes described in JP-A-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like; And the cyanine dyes described in British Patent No. 434,875.

As a dye, US Pat. No. 5,156,
No. 938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924;
No. 42645 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt described in JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363
Nos. 59-84248, 59-84249, 59-146063, and 59-146061 and pyrylium compounds described in JP-A-59-2161.
No. 46, a cyanine dye disclosed in U.S. Pat. No. 4,283,4.
No. 75, pentamethine thiopyrylium salts and the like, and pyrilium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702;
ht III-178, Epollight III-130, E
Pollite III-125 and the like are particularly preferably used.

Another particularly preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight, in the case of dyes, Particularly preferred is 3.1.
It can be added to the printing plate material at a ratio of 10 to 10% by weight. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered. If the amount exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the recording layer is deteriorated. These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto. If it is a separate layer, it is desirable to add it to a layer adjacent to the layer containing a substance which substantially reduces the solubility of the binder when it is thermally decomposable and does not decompose. The dye or pigment and the binder resin are preferably in the same layer, but may be in different layers.

Various additives can be added to the positive photosensitive composition of the present invention, if necessary. For example, a thermally decomposable substance such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound, and a substance that substantially lowers the solubility of an alkali water-soluble polymer compound when not decomposed is used in combination. This is preferable from the viewpoint of improving the dissolution inhibiting property of the image area in the developer. As onium salts, diazonium salts,
Examples thereof include ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like.

Suitable onium salts used in the present invention include, for example, SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TS Bal et a
1, Polymer, 21, 423 (1980), JP-A-5-158230
No. 4,069,055 diazonium salt described in U.S. Pat.
No. 4,069,056, ammonium salt described in the specification of JP-A-3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc. Co.
nf.Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JVCrivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988), EP 104,143, U.S. Patent 339,049
No. 410,201, JP-A-2-150848, JP-A-2-2-2965
Iodonium salt described in No. 14, JVCrivello et al, P
olymer J. 17, 73 (1985), JV Crivello et al. J.
Org.Chem., 43, 3055 (1978), WR Watt et al, J. P.
olymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JV Crivello et al, Polymer Bull., 14, 279 (198
5), JV Crivello et al, Macromorecules, 14 (5)
, 1141 (1981), JV Crivello et al, J. Polymer Sc
i., Polymer Chem.Ed., 17, 2877 (1979), European Patent Nos. 370,693, 233,567, 297,443, 297,44
No. 2, U.S. Pat.Nos. 4,933,377, 3,902,114, 41
0,201, 339,049, 4,760,013, 4,734,44
No. 4, No. 2,833,827, German Patent No. 2,904,626, No. 3,
Nos. 604,580 and 3,604,581, sulfonium salts,
JV Crivello et al, Macromorecules, 10 (6), 1307
(1977), JV Crivello et al, J. Polymer Sci., Pol
selenonium salt described in ymer Chem. Ed., 17, 1047 (1979), CS Wen et al, Teh, Proc. Conf. Rad. Curing
ASIA, p478 Tokyo, Oct (1988).

In the present invention, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230. Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, o-quinonediazide helps the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the fact that o-quinonediazide itself changes to an alkali-soluble substance. O used in the present invention
Examples of the quinonediazide compound include: "Wright-Sensitive Systems" by Coser (John Wil
ey & Sons. Inc.) pp. 339-352 can be used. Particularly, sulfonic esters or sulfonic amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds can be used. It is suitable. Also, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403. Esters of the benzoquinones described in U.S. Patents 3,046,120 and 3,188,210
Esters of (1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride with a phenol-formaldehyde resin are also suitably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride with pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96
No. 575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, and 3,674,495
No. 3,785,825; British Patent No. 1,227,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
No. 1,330,932, and German Patent No. 854,890, etc. can be mentioned.

The addition amount of the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 3% by weight, based on the total solids of the printing plate material.
The range is 0% by weight. These compounds can be used alone, but may be used as a mixture of several kinds.

The counter ions of the onium salts 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, paratoluenesulfonic acid and the like can be mentioned. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

The amount of additives other than the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight. It is preferable that the additive and the binder of the present invention are contained in the same layer.

For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols and organic acids can be used in combination. US Patent No. 4,115,1 discloses cyclic acid anhydrides.
No. 28, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6
-Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol,
p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ',
4 "-trihydroxytriphenylmethane, 4,4 ',
3 ", 4" -tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane and the like can be mentioned. Further, examples of organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, carboxylic acids and the like described in JP-A-60-88942 and JP-A-2-96755. There are 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-
Examples thereof include 1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.

The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the image recording material is 0.05 to 2%.
It is preferably 0% by weight, more preferably 0.1 to 15% by weight, most preferably 0.1 to 10% by weight. Also,
In the image recording material of the present invention, Japanese Patent Application Laid-Open No. 62-251740 is used in order to increase the stability of processing under development conditions.
Non-ionic surfactants described in JP-A-59-208104 and JP-A-3-208514.
No. 4, JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether and the like. Specific examples of the surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N
-Tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo KK) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight. In the image recording material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image coloring agent can be added.

Representative examples of the printing-out agent include a combination of a compound that releases an acid upon exposure to light (photoacid releasing agent) and an organic dye capable of forming a salt.
Specifically, JP-A-50-36209 and JP-A-53-81
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A Nos. 28-28, and JP-A-53-36223 and JP-A-54-747.
No. 28, No. 60-3626, No. 61-143748
And combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A Nos. 61-151644 and 63-58440. 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 include oil-soluble dyes and basic dyes, in addition to salt-forming organic 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 Industries, 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-62-29
The dye described in Japanese Patent No. 3247 is particularly preferred as a colorant for an image. These dyes are used in an amount of 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the image recording material.
It can be added to the image recording material at a ratio of about 3% by weight.

Further, a plasticizer may be added to the image recording material of the present invention, if necessary, in order to impart flexibility 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, oligomers and polymers of acrylic acid or methacrylic acid, and the like are used. The image recording material of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution on a suitable support. As the solvent used here, 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, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene And the like, but 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 the coating method, 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. In the recording layer of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. The addition amount is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight of the whole image recording material.

The support used in the present invention is a dimensionally stable plate. As such a support, for example,
Paper, plastics (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloys), zinc, iron, copper, etc. metal plates, etc. are used. Is preferred from the viewpoint of the effect. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The different elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth,
There are nickel, titanium, and the like. The content of the foreign element in the alloy is 10% by weight or less. Aluminum suitable for 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 a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1. It is 1 mm to 0.6 mm.

When an aluminum plate is used as the support, the aluminum plate is roughened in order to increase the adhesion between the aluminum plate and the layer applied thereon. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing rolling oil on the surface is performed.
Methods for roughening the aluminum plate include a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively melting the surface. As the mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of utilizing alternating current 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 necessary to increase the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte that forms 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. Anodizing treatment conditions vary depending on the electrolyte used, and thus cannot be specified unconditionally. Generally, 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 , voltage 1
-100V, electrolysis time 10 seconds-5 minutes.

The amount of the anodic oxide film is preferably 1.0 g / m ² or more, more preferably 2.0 to 6.0 g / m ^2.
Range. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily scratched, and the ink adheres to the scratched area during printing. "Scratch dirt" easily occurs. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. Examples of the hydrophilic treatment preferably used in the present invention include U.S. Pat. Nos. 2,714,066 and 3,1.
Nos. 81,461, 3,280,734 and 3,9
There is an alkali metal silicate (for example, an aqueous solution of sodium silicate) as disclosed in Japanese Patent No. 02,734. In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. In addition,
Potassium fluorozirconate disclosed in U.S. Pat. No. 2,220,632, and polyvinyl as disclosed in U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272. A method of treating with phosphonic acid is used.

It is preferable to provide an organic undercoat layer on the photosensitive lithographic printing plate of the present invention before coating the photosensitive layer, in order to reduce the remaining photosensitive layer in the non-image area. As the organic compound used in the organic undercoat layer, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, organic phosphinic acid 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 hydrochloride of triethanolamine A having a hydroxyl group such as Selected from emissions hydrochloride salt. These may be used alone or as a mixture of two or more.

Further, an organic undercoat layer containing at least one compound selected from the group of organic polymer compounds having a structural unit represented by the following general formula (XIII) is also preferable.

Embedded image R ¹ represents a hydrogen atom, a halogen atom or an alkyl group;
R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group,
Halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -OR ^4, -COOR ^5, -CO
Represents NHR ⁶ , —COR ⁷ or —CN, or R
² and R ³ may combine to form a ring, and R ^{4 to} R ⁷
Each independently represents an alkyl group or an aryl group,
X represents a hydrogen atom, a metal atom, NR ⁸ R ⁹ R ¹⁰ R ¹¹ ;
R ^{8 to} R ¹¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, or R ⁸ and R ⁹ may combine to form a ring; Represents an integer of 1 to 3.

This organic undercoat layer can be provided by the following method. That is, water or methanol, ethanol,
A method in which a solution obtained by dissolving the above organic compound in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum plate, and the coating film is dried, and water, or an organic solvent such as methanol, ethanol or methyl ethyl ketone, or a method thereof. A method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved in a mixed solvent of the above to adsorb the organic compound, and then the aluminum plate is washed with water or the like and dried. 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. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight.
% By weight and an immersion temperature of 20 to 90 ° C., preferably 2 to 90 ° C.
5 ° C. to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is pH 1
It can be used in the range of ~ 12. The pH can be adjusted with a basic substance such as ammonia, triethylamine and potassium hydroxide, and an acidic substance such as hydrochloric acid and phosphoric acid. Further, a yellow dye can be added to the solution for improving the tone reproducibility of the photosensitive lithographic printing plate.

The coating amount of the organic undercoat layer after drying is from 2 to 20.
0 mg / m ² is suitable, preferably 5 to 100 mg.
/ M ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. In addition, 200mg / m
^{The same} applies even if it is larger than ² . A back coat is provided on the back surface of the support as necessary. Examples of such a back coat include a coating composed of an organic polymer compound described in JP-A-5-45885 and a metal oxide obtained by hydrolysis and polycondensation of an organic or inorganic metal compound described in JP-A-6-35174. Layers are preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC
_{2 H 5) 4, Si (} OC 3 H 7) 4, Si (OC
An alkoxy compound of silicon such as ₄ H ₉ ) ₄ is particularly preferable because it is inexpensive and easily available, and a metal oxide coating layer obtained therefrom has excellent developer resistance.

Examples of the light source of the actinic ray used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
The radiation includes an electron beam, an X-ray, an ion beam, a far infrared ray, and the like. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium-neon laser, an argon laser, a krypton laser, a helium-cadmium laser, and a KrF excimer laser.
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.

Next, the developer used in the present invention will be described. In this specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher. Preferred as a developer for the photosensitive lithographic printing plate of the present invention is an alkaline aqueous solution containing substantially no organic solvent. Specifically, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, dibasic sodium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, bicarbonate Aqueous solutions such as sodium, potassium carbonate, aqueous ammonia and the like are suitable. More preferably, the developer contains (a) at least one saccharide selected from non-reducing sugars, and (b) at least one base, and has a pH in the range of 9.0 to 13.5.

The non-reducing sugar, which is a developer preferably used in the present invention, will be described. The non-reducing sugar is a saccharide that does not have an advantageous aldehyde group or ketone group and does not exhibit reducing properties. Are classified as trehalose-type oligosaccharides, glycosides in which a reducing group of a saccharide is bonded to a non-saccharide, and sugar alcohols obtained by hydrogenating and reducing saccharides, all of which are suitably used in the present invention. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D, L
-Arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L
-Tallit, zusilit, allozurshit and the like. Reductants obtained by hydrogenation of maltitol and oligosaccharides obtained by hydrogenation of disaccharides (reduced water syrup)
Is preferably used. Among these, non-reducing sugars which are particularly preferred are sugar alcohols and saccharose, and D-sorbitol, saccharose and reduced starch syrup are particularly preferred since they have a buffering action in an appropriate pH range and are inexpensive. These non-reducing sugars can be used alone or in combination of two or more, and their ratio in the developer is 0.1%.
It is preferably from 1 to 30% by weight, more preferably from 1 to 20% by weight. If this ratio is less than 0.1% by weight, a sufficient buffering effect cannot be obtained. When a reducing sugar is used in combination with a base, the color changes to brown over time,
Is also gradually lowered, and thus the developing property is deteriorated.

As the base to be combined with the non-reducing sugar, conventionally known alkaline agents can be used. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate And inorganic alkali agents such as potassium bicarbonate, ammonium bicarbonate, sodium sulphate, potassium sulphate and ammonium sulphate. Also,
Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine And organic alkali agents such as ethylenediamine and pyridine. These alkali agents are used alone or in combination of two or more. Of these, sodium hydroxide and potassium hydroxide are preferred. The reason is that by adjusting these amounts with respect to the non-reducing sugar, the pH can be adjusted in a wide pH range. Also, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable since they themselves have a buffering action. These alkaline agents are added so that the pH of the developing solution is in the range of 9.0 to 13.5, and the amount of addition is determined depending on the desired pH, the type and the amount of non-reducing sugar, but more preferable pH The range is from 10.0 to 13.2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. The weak acid used as such a buffer is preferably one having a dissociation constant (pKa) of 10.0 to 13.2. Such a weak acid can be obtained from IONIS issued by Pergamon Press.
ATTION CONSTANTS OF ORGANl
C ACIDS IN AQUEOUS SOLUTI
ON, etc., for example, 2,
2,3,3-tetrafluoropropanol-1 (pKa
12.74), trifluoroethanol (12.3)
7), alcohols such as trichloroethanol (12.24) and pyridine-2-aldehyde (12.6).
8), aldehydes such as pyridine-4-aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), Gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (11.94), 1,2,2 4-trihydroxybenzene (11.82), hydroquinone (11.56),
Pyrogallol (11.34), o-cresol (1)
0.33), resorcinol (11.27), P-cresol (10.27), m-cresol (10.
09) and other compounds having a phenolic hydroxyl group, 2-butanone oxime (12.45) and acetoxime (1).
2.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (1)
1.9), ethanediamide dioxime (11.3)
7), oximes such as acetophenone oxime (11.35), adenosine (12.56), inosine (12.5), guanine (12.3), cytosine (1)
2.2), hypoxanthine (12.1), xanthine (11.9) and other nucleic acid-related substances, as well as diethylaminomethylphosphonic acid (12.32), 1-amino-
3,3,3-trifluorobenzoic acid (12.29);
Isopropylidene diphosphonic acid (12.10), 1,
1-ethylidene diphosphonic acid (11.54), 1.1
1-hydroxyethylidene diphosphonic acid (11.5
2), benzimidazole (12.86), thiobenzamide (12.8), picoline thioamide (1)
2.55) and barbituric acid (12.5).

Preferred among these weak acids are sulfosalicylic acid and salicylic acid. As a base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used. These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination. Various surfactants and organic solvents can be added to the developer as needed for the purpose of accelerating the developability, dispersing the development residue, and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and glycerin fatty acid partial esters. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester , Polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides,
Nonionic surfactants such as N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts , Alkane sulfonates, dialkyl sulfosuccinate salts, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates,
Alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil Sulfuric acid salts of fatty acid-resistant alkyl esters, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, fatty acid monoglyceride sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, polyoxyethylene styryl phenyl ether sulfate salts , Alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, Partially saponified products of Tylene / ice-free maleic acid copolymer, partially saponified products of olefin / maleic anhydride copolymer, anionic surfactants such as naphthalene sulfonate formalin condensates, alkylamine salts, tetrabutyl Quaternary ammonium salts such as ammonium bromide, polyoxyethylene alkylamine salts, cationic surfactants such as polyethylene polyamine derivatives, carboxybetaines, aminocarboxylic acids,
Examples include amphoteric surfactants such as sulfobetaines, aminosulfates, and imidazolines. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorine-based surfactants include anionic types such as perfluoroalkylcarboxylates, perfluoroalkylsulfonates, and perfluoroalkylphosphates; amphoteric types such as perfluoroalkylbetaines; and perfluoroalkyltrimethylammonium salts. Perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl group, hydrophilic group and lipophilic Non-ionic types such as a group-containing oligomer, a perfluoroalkyl group and a lipophilic group-containing urethane are exemplified. The above-mentioned surface consolidating agents can be used alone or in combination of two or more kinds.
It is added in the range of weight%.

Various developing stabilizers are used in the developing solution. Preferred examples thereof are described in JP-A-6-2820.
Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-79, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. There are water-soluble amphoteric polyelectrolytes that have been used. Further, an organic boron compound to which an alkylene glycol is added as disclosed in JP-A-59-84241, JP-A-60-111246
JP-A-60-1 discloses a polyoxyethylene-polyoxypropylene block polymerization type water-soluble surfactant described in
No. 29750, polyoxyethylene, an alkylenediamine compound substituted with polyoxypropylene, and a weight average molecular weight of 300 described in JP-A No. 61-215554.
The above polyethylene glycol, JP-A-63-1758
No. 58, a fluorine-containing surfactant having a cationic group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol described in JP-A-2-39157, and a water-soluble polyalkylene compound And the like.

Although the developing solution of the present invention does not substantially contain an organic solvent, an organic solvent is added if necessary.
As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol,
2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methokinebenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methyl Cyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

A reducing agent can be further added to the developer. This is to prevent the printing plate from being stained, and is particularly effective when developing a negative image recording material containing a photosensitive diazonium salt compound. Preferred organic reducing agents include phenolic compounds such as thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcin, and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sulfurous acid, bisulfite, phosphorous acid,
Examples thereof include sodium salts, potassium salts, and ammonium salts of inorganic acids such as hydrogen phosphite, dihydrophosphite, thiosulfate, and dithionite. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

The developing solution may further contain an organic carboxylic acid. Preferred organic carboxylic acids have 6 to 6 carbon atoms.
20 aliphatic carboxylic acids and aromatic carboxylic acids.
Specific examples of aliphatic carboxylic acids include caproic acid,
Enantylic acid, caprylic lauric acid, myristic acid,
There are palmitic acid, stearic acid and the like, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. As the aromatic carboxylic acid, a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like, specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid,
p-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5
-Dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, There are 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like, and hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to increase the water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited,
If the amount is less than 0.1% by weight, the effect is not sufficient. If the amount is more than 10% by weight, the effect cannot be further improved, and dissolution may be hindered when another additive is used in combination. Therefore, the preferable addition amount is 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, based on the developer used.
4% by weight. The developer may further contain a preservative, a colorant, a thickener, an antifoaming agent, a water softener, and the like, if necessary. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid,
Aminopolycarboxylic acids such as hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts; aminotri (methylene Phosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxyethane-1,1
-Diphosphonic acids and their sodium, potassium and ammonium salts.

The optimum value of such a water softening agent varies depending on the chelating power, the hardness of the hard water used and the amount of the hard water.
The range is from 0.01 to 5% by weight, more preferably from 0.01 to 0.5% by weight. If the amount is less than 0.01% by weight, the intended purpose is not sufficiently achieved, and if the amount is more than 0.5% by weight, adverse effects on the image portion such as color omission appear. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution in which the content of water is smaller than that at the time of use, and is diluted with water at the time of use. In this case, the concentration is suitably such that the components do not separate or precipitate. As the developer for the image recording material of the present invention, the developer described in JP-A-6-282079 can also be used.
This is SiO ₂ / M ₂ O (M represents an alkali metal)
Is a developer containing an alkali metal silicate having a molar ratio of 0.5 to 2.0 and a water-soluble ethylene oxide adduct obtained by adding 5 mol or more of ethylene oxide to a sugar alcohol having 4 or more hydroxyl groups. Sugar alcohol reduces the aldehyde group and ketone group of the sugar to the first,
It is a polyhydric alcohol corresponding to a secondary alcohol group. Specific examples of sugar alcohols include D, L-
Trait, erythritol, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L-tallit, zulcit, allozulcit, and the like. Also included are condensed di, tri, tetra, penta and hexaglycerin. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxod adduct as needed, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more. The addition amount of these water-soluble ethylene oxide addition compounds is suitably from 0.001 to 5% by weight, more preferably from 0.001 to 2% by weight, based on the developer (working solution).

The above-mentioned various surfactants and organic solvents can be further added to the developer, if necessary, for the purpose of accelerating the developability, dispersing the developing residue, and increasing the ink affinity of the printing plate image area. . The image recording material developed with a developer having such a composition is subjected to post-treatment with washing water, a rinsing solution containing a surfactant or the like, a finisher containing a gum arabic or a starch derivative, or a protective gum solution as a main component. . In the post-processing of the image recording material of the present invention, 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 each of which is pumped up while pumping an exposed printing plate horizontally. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method is also 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 case where the image recording material of the present invention is used as a photosensitive lithographic printing plate will be described. If the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has an unnecessary image portion (for example, a film edge mark of the original film), the unnecessary image portion may be removed. The necessary image portion is erased. 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 it 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 process after applying a desensitized gum if desired, but if a lithographic printing plate with higher printing durability is desired, a burning treatment is required. Is applied. When burning a lithographic printing plate, before burning, the Japanese Patent Publication No. 61-251
No. 8, No. 55-28062, JP-A-62-31859.
And JP-A-61-159655.

As the method, a method of applying the surface-regulating liquid on a lithographic printing plate using a sponge or absorbent cotton, or a method of immersing the printing plate in a vat filled with the surface-regulating liquid and applying the liquid, or an automatic coater Is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application 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 heated to a high temperature by a burning processor (for example, a burning processor: BP-1300 sold by Fuji Photo Film Co., Ltd.). . The heating temperature and time in this case depend on the type of the components forming the image, but are preferably in the range of 180 to 300 ° C. and 1 to 20 minutes. The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary, but a surface conditioning liquid containing a water-soluble polymer compound or the like is used. In such a case, 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.

[0110]

Hereinafter, the present invention will be described with reference to Examples.
The scope of the present invention is not limited to these examples. Synthesis Example 1 (Polymer Compound 1) 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. 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 the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes. In this reaction mixture,
51.7 g of p-aminobenzenesulfonamide (0.3
0 mol) 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 a precipitate, which was then slurried with 500 ml of water. The slurry was filtered, and the obtained solid was dried to obtain N-.
A white solid of (p-aminosulfonylphenyl) methacrylamide was obtained (yield 46.9 g).

Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
92 mol), and 2.94 g (0.02 g) of ethyl methacrylate.
58 mol), 0.80 g (0.015 g) of acrylonitrile
Mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. To this mixture, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1
5 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. To this reaction mixture, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g of ethyl methacrylate, and 0.8 of acrylonitrile were further added.
0 g, N, N-dimethylacetamide and V-65
0.15 g of the mixture was added dropwise from the dropping funnel over 2 hours. After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled. The obtained mixture was poured into 2 liters of water while stirring the water, and the mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15g
A white solid was obtained. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography and found to be 53,000.

Synthesis Example 2 (Polymer compound 2) 25.9 g (0.36 mol) of acrylic acid was placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile were added, and the mixture was stirred while cooling in an ice water bath. To this mixture was added triethylamine.
4 g (0.36 mol) was added dropwise over about 1 hour using a dropping funnel. After the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes. 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added to the reaction mixture, 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 is filtered to remove the precipitate,
This was slurried with 500 ml of water, the slurry was filtered, and the obtained solid was dried to obtain N- (p
A white solid of (-aminosulfonylphenyl) acrylamide was obtained (yield 42.3 g).

Next, 5.08 g (0.022 g) of N- (p-aminosulfonylphenyl) acrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
4 mol), 1.96 g (0.020 g) of methyl methacrylate
Mol), 0.96 g (0.018 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide,
The mixture was stirred while being heated to 65 ° C. by a water bath.
0.15 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this mixture.
Was added and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further charged with 5.08 g of N- (p-aminosulfonylphenyl) acrylamide, 1.96 g of methyl methacrylate, 0.96 g of acrylonitrile,
N, N-dimethylacetamide and V-65 0.15
g of the mixture was dropped by a dropping funnel over 2 hours.
After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled. The obtained mixture was added to 2 liters of water while stirring the water, and the mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15 g of a white solid was obtained. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography and found to be 47,000.

Synthesis Example 3 (Polymer compound 3) 8.6 g (0.036 mol) of N- (p-toluenesulfonyl) -methacrylamide and methacrylic acid were placed in a 20 ml three- necked flask equipped with a stirrer, a condenser and a dropping funnel. 1.20 g (0.012 mol) of methyl, 0.64 g (0.012 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. 0.15 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. To this reaction mixture was further added a mixture of 8.6 g of N- (p-toluenesulfonyl) -methacrylamide, 1.20 g of methyl methacrylate, 0.64 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of V-65. The solution was dropped with a dropping funnel over time. 65 ° C after completion of dropping
The resulting mixture was stirred for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled. The obtained mixture was added to 2 liters of water while stirring the water, and the mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15 g of a white solid was obtained. The weight average molecular weight (polystyrene standard) of the polymer compound measured by gel permeation chromatography was 55,000.

(Examples 1 to 5) Aluminum having a thickness of 0.3 mm
Washing of aluminum plate (material 1050) with trichlorethylene
And degrease, then use a nylon brush and 400 mesh
Mis-grain this surface with a water suspension and wash well with water.
Washed. This plate was washed at 25 ° C with 25% aqueous sodium hydroxide.
Immerse in the solution for 9 seconds to perform etching, wash with water,
Was immersed in 20% nitric acid for 20 seconds and washed with water. Sand at this time
The amount of etching on the dressing surface is about 3 g / m ^TwoMet. Next
This plate was subjected to a current density of 15 A / d using 7% sulfuric acid as an electrolyte.
m^Two3g / m^TwoAfter the DC anodic oxide coating of
And dried to obtain a substrate A. Substrate A is coated with the following undercoat liquid
Cloth was applied and the coating film was dried at 90 ° C. for 1 minute to obtain a substrate B. After drying
10mg / m^TwoMet.Undercoat liquid β-alanine 0.5 g methanol 95 g water 5 g Substrate A was treated with a 2.5 wt% aqueous solution of sodium silicate at 30 ° C.
Treat for 10 seconds, apply the following undercoat liquid, and coat the film at 80 ° C.
After drying for 15 seconds, a substrate C was obtained. The coating amount of the coating after drying is
15mg / m^TwoMet.Undercoat liquid The following copolymer having a molecular weight of 28,000 0.3 g Methanol 100 g Water 1 g Coating amount of the following photosensitive liquids 1 to 4 on the obtained substrate B
Is 1.8 g / m^TwoLithographic printing plate B1
4 was obtained.

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Photosensitive solution 1 Polymer compound 1 0.7 g m, p-cresol novolak (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) 0.3 g Sulfone compound (II-1) 0.08 g p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye A 0.017 g Victoria pure blue BOH dye having a counter ion of 1-naphthalenesulfonic acid anion 0 0.015 g Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) 0.05 g γ-butyl lactone 2 g methyl ethyl ketone 20 g 1-methoxy-2-propanol 1 g

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[0117]

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Photosensitive solution 2 Polymer compound 2 0.3 g m, p-cresol novolak (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) 0.7 g Sulfone compound (II-4) 0.26 g p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye B 0.017 g Sulfonate anion dye 0.015 g Megafax F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) 0.05 g γ-butyl lactone 2 g methyl ethyl ketone 20 g 1-methoxy-2-propanol 1 g

[0119]

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[0120]

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Photosensitive solution 3 Polymeric compound 3 0.9 g m, p-cresol novolak (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) 0.1 g Sulfone compound (II-14) 0.16 g p-Toluenesulfonic acid 0.003 g Tetrahydrophthalic anhydride 0.03 g Cyanine dye C 0.008 g Dye in which the counter ion of Victoria Pure Blue BOH is 1-naphthalenesulfonic acid anion 0 .015 g Megafax F-177 (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) 0.05 g γ-butyl lactone 2 g methyl ethyl ketone 20 g 1-methoxy-2-propanol 1 g

[0122]

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[0123]

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Photosensitive solution 4 Copolymer of benzyl methacrylate and methacrylic acid 0.9 g (molar ratio 72:28, weight average molecular weight 70,000) p-cresol / phenol / formaldehyde novolak resin (p-cresol / phenol = 5) / 5, weight average molecular weight 7,000, unreacted cresol and phenol 0.5% by weight) 0.1 g disulfone compound (I-3) 0.05 g p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0. 03g Cyanine dye D 0.017g 4- (p-Hydroxybenzoylaminophenyl) -2,6-bis (trichloromethyl) -s-triazine 0.01g The counter ion of Victoria Pure Blue BOH is converted to anion of 1-naphthalenesulfonic acid. Dye 0.015g Megafac F-177 (Fluorine surfactant, manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g γ-butyl lactone 2 g Methyl ethyl ketone 20 g 1-methoxy-2-propanol 1 g

[0125]

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[0126]

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(Comparative Example 1) and (Comparative Example 2) The following photosensitive liquids 5 and 6 were applied to the substrate B at an amount of 1.8 g / m 2.
^Then , lithographic printing plates B5 and B6 were obtained. Photosensitive solution 5 Polymer compound 1 0.7 g m, p-cresol novolak (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight) 0.3 g p-toluene Sulfonic acid 0.003 g Tetrahydrophthalic anhydride 0.03 g Cyan dye A 0.017 g Dye in which the counter ion of Victoria Pure Blue BOH is converted to 1-naphthalenesulfonic acid anion 0.015 g Megafac F-177 (Dainippon Ink & Chemicals, Inc.) 0.05 g g-butyl lactone 2 g methyl ethyl ketone 20 g 1-methoxy-2-propanol 1 g

Photosensitive solution 6 Esterified product of naphthoquinone-1,2-diazido-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) Copolymer of 1.10 g of N- (p-aminosulfonylphenyl) methacrylamide and methyl methacrylate (described in Synthesis Example 1 in EP 330,239 (A ₂ )) 2 -(P-methoxyphenyl) -4,6-bis 0.02 g (trichloromethyl) -s-triazine oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01 g 2,6-di-t-butyl- 4- [5- (2,6-di-0.01422 g t-butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl] Opyrilium tetrafluoroborate (compound described in U.S. Pat. No. 4,283,475) Megafac F-177 0.06 g (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 10 g Methyl cellosolve 10g

The obtained planographic printing plates B-1 to B- of the present invention
Output 5 and lithographic printing plates B-5 and B-6 of Comparative Example 5
00 mW, wavelength 830 nm, beam diameter 17 μm (l / e
² ) After exposure using a semiconductor laser at a main scanning speed of 5 m / sec, a developer DP-4 manufactured by Fuji Photo Film Co., Ltd.
And a PS processor 900 manufactured by Fuji Photo Film Co., Ltd., which contains a rinse liquid FR-3 (diluted 1: 7).
Developed using VR. At that time, DP-4 was used in two levels, one diluted 1: 8 and one diluted 1:12, and the exposure amount required for image formation was measured with each developer, and the difference (development latitude) was measured. Was recorded. The smaller the numerical value shown in the table, the better the development latitude.
If it is 0 mJ / cm ² or less, it is at a practical level.

[0130]

[Table 1]

From Table 1, the planographic printing plates B-1 to B-4 using the disulfone or the sulfone compound show B-5 and B
As compared with −6, the developing latitude was excellent, and it can be seen that the developing latitude was at a practical level. (Examples 5 to 8, Comparative Examples 3 to 4) Except that the substrate B was changed to the substrate C, lithographic printing plates C-1 to C-6 were prepared in the same manner as in Examples 1 to 4 and Comparative Examples 1 and 2. Obtained. The lithographic printing plates C-1 to C-4 of the present invention and the lithographic printing plates C-5 and C-6 of the comparative example were obtained by using a semiconductor laser having an output of 500 mW, a wavelength of 830 nm, and a beam diameter of 17 μm (l / e ² ). After exposure at a main scanning speed of 5 m / sec, two types of developing solutions (developing solution 1 and developing solution 2) and a rinsing solution FR-3 (diluted 1: 7) having the following composition and different dilution ratios were used. Was developed using PS Processor 900VR manufactured by Fuji Photo Film Co., Ltd. At that time, the exposure amount required for image formation was measured with each developing solution, and the difference (development latitude) was recorded.

Developer 1 D-sorbitol 5.1 parts by weight Sodium hydroxide 1.1 parts by weight Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by weight Water 93.9 parts by weight Developer 2 D- Sorbitol 5.1 parts by weight Sodium hydroxide 1.1 parts by weight Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by weight Water 140.7 parts by weight

[0133]

[Table 2]

From Table 2, it can be seen that the lithographic printing plates C-1 to C-4 using the disulfone or the sulfone compound have excellent development latitude as compared with the printing plates C-5 and C-6 of the comparative examples.

[0135]

According to the present invention, it is possible to provide an image recording material which can use a conventional processing device or printing device as it is, can make a plate directly from digital data of a computer or the like, and has a wide development latitude.

Claims (1)

[Claims] 1. A positive photosensitive composition for an infrared laser containing at least an alkali-soluble polymer compound and a substance that absorbs light and generates heat, wherein the compound (I) or (II) represented by the following formula: The photosensitive composition as described above, comprising: ## STR1 _{^{R 1 -SO 2 -SO 2 -R 2}} (I) ## STR2 ## _{^{R 1 -SO 2 -R 2 (II}} ) formula, R ¹ and R ² may be the same or different, substituted Or an unsubstituted alkyl group, alkenyl group, or aryl group.