JPH11102066A - Planographic printing plate material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the shelf stability of a printing plate material and to ensure high sensitivity by forming a photosensitive layer contg. a compd. capable of generating acid when irradiated with active light, a compd. having a bonding part which can be decomposed by the acid, an IR absorber and an acid propagator on a substrate. SOLUTION: A photosensitive layer contg. a compd. capable of generating acid when irradiated with active light, a compd. having a bonding part which can be decomposed by the acid or a compd. which can be made alkali-insoluble in the presence of the acid, an IR absorber and an acid propagator is formed on a substrate. The acid propagator is a compd. substd. by the residue of relatively strong acid and this compd. relatively easily causes elimination reaction and generates the acid. The elimination reaction can be drastically activated by acid catalyzed reaction and the acid formation by thermochemical reaction is easily enabled in the absence of the acid. Since the acid propagator is combined with the light-acid generating agent, the rate of sensitization is increased.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate material having a so-called positive type photosensitizer which is solubilized by actinic light or a so-called negative type photosensitizer which is insolubilized by actinic light. The present invention relates to a lithographic printing plate material capable of forming an image by exposure to infrared light such as a semiconductor laser.

[0002]

2. Description of the Related Art Conventionally, a composition for a photosensitive lithographic printing plate having a positive photosensitive layer solubilized by actinic light has been disclosed.
Also, a composition for a photosensitive lithographic printing plate having a negative photosensitive layer, which is insolubilized by actinic light, is known.

[0003] As a photosensitive material using a positive composition which is solubilized by irradiation with actinic light, an image forming material having a photosensitive layer containing an acid generator and an acid-decomposable compound is known. For example, U.S. Pat. No. 3,779,779 discloses a photosensitive composition containing a compound having an orthocarboxylic acid or a carboxylic amide acetal group.
JP-A-3-133429 discloses a photosensitive composition containing a compound having an acetal in the main chain.
No. 49 discloses a composition containing a compound having a silyl ether group. These are all sensitive to ultraviolet light, and are alkali-solubilized by exposure to ultraviolet light to form non-image areas, and unexposed areas form image areas.

[0004] As the negative type, for example,
Nos. 7364 and 52-3216 disclose a photosensitive material which forms an image area by irradiating active light with photopolymerization or photocrosslinking by irradiating with active light, and the exposure means is ultraviolet light exposure as in the positive type. Further, US Pat.
No. 99 discloses a technique in which a photosensitive material containing an acid generator, an acid crosslinking agent (resole resin), a binder (novolak resin), and an infrared absorber is exposed to infrared light to make the exposed portion alkali-insoluble. .

On the other hand, in recent years, there has been a demand for improved work efficiency. In response to the trend in the plate making industry, in order to easily perform conventional manual and time-consuming editing work by software using a computer, a plate making method that can be digitally recorded by an inexpensive and compact infrared semiconductor laser, that is, CTP (computer to plate) ) Is in the spotlight.

[0006] However, although the CTP greatly improves the efficiency of the editing operation itself, the exposure time is not short enough, and therefore an improvement in sensitivity is desired. As a measure for improving the sensitivity, it is easy to increase the amount of an initiator system such as an acid generator and an infrared (IR) absorber. However, the amount of the acid generator is actually increased by the chemical amplification type as described above. In the case of CTP, there is a tendency that the preservability of the printing plate tends to decrease, and in the IR exposure system, an increase in the amount of the IR absorber causes a decrease in sensitivity which is presumed to be caused by an increase in the dissolution suppressing effect. Improvement was sought.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve the storage stability of a plate material even in an IR exposure system, and to provide a highly sensitive positive or negative type. Is to provide a lithographic printing plate.

[0008]

The above object of the present invention has been attained by the following constitutions.

<1> A photosensitive layer containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond decomposable by an acid, an infrared absorber and an acid multiplying agent is provided on a support. A lithographic printing plate material characterized in that:

<2> Provided on a support is a photosensitive layer containing a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond decomposable by the acid, an infrared absorber, and a diazo compound. A lithographic printing plate material comprising:

<3> A photosensitive layer containing, on a support, a compound capable of generating an acid upon irradiation with actinic rays, a compound capable of being insolubilized in an alkali in the presence of an acid, an infrared absorber and an acid multiplying agent. A lithographic printing plate material characterized by comprising:

<4> Photosensitivity on a support containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of being insolubilized in an alkali in the presence of an acid, an infrared absorber, and a diazo compound A lithographic printing plate material comprising a layer.

In a preferred embodiment, the acid proliferating agent has a structure represented by any one of the above formulas (1) to (4), the diazo compound has a structure represented by the above formula (5) or (6); The compound having a bond that can be decomposed by an acid has a structure represented by the general formula (7) or (8), and the compound that can be insolubilized in an alkali in the presence of the acid has a methylol group. A compound that can be insolubilized with respect to alkali in the presence of the acid is at least one of a melamine resin and a resol resin, the infrared absorber is a cyanine dye, and the photosensitive layer has a wavelength of 700 to 2,000 nm. To respond to

That is, the inventors of the present invention have proposed a system which can form an image by exposure to infrared rays.
As a result of intensive studies to achieve high sensitivity, the present inventors have found that the above object can be achieved by incorporating an acid multiplying agent in the photosensitive layer, or by incorporating a diazo compound in the photosensitive layer, leading to the present invention. It has a performance capable of solving the above-mentioned problem by exposure to a system using infrared rays.

Hereinafter, the present invention will be described in detail.

[1] Lithographic printing plate material The lithographic printing plate material of the present invention can be broadly classified into an acid-proliferating agent-containing type and a diazo-based compound-containing type according to its form, and both have a positive type and a negative type.

(1) Acid-Proliferating Agent-Containing Type A lithographic printing plate material of this type comprises a support capable of generating a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond capable of being decomposed by an acid, or a compound of an acid. It is provided with a photosensitive layer containing a compound which can be made insoluble in alkali in the presence thereof, an infrared absorbing agent and an acid multiplying agent.

In the present invention, the acid proliferating agent is a compound substituted with a relatively strong acid residue, and is a compound which generates an acid by causing an elimination reaction relatively easily. Therefore, this elimination reaction can be largely activated by an acid-catalyzed reaction, and is stable in the absence of an acid, but can be easily generated by a thermochemical reaction in the presence of an acid. Becomes By combining an acid multiplying agent having such properties with a photoacid generator, it becomes possible to obtain a photoreactive composition having a remarkably improved photospeed. It is decomposed by an acid-catalyzed reaction to generate an acid again (ZOH in the following general formula). One or more acids increase in one reaction, and the reaction accelerates with the progress of the reaction. Since the generated acid itself induces self-decomposition, the generated acid has an acid dissociation constant, (pKa) of 3 or less, and particularly preferably 2 or less. If the acid is weaker than this, self-decomposition cannot be caused. Such acids include dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid,
Triphenylphosphonic acid and the like can be mentioned. Specifically, the following compounds can be exemplified.

First, an organic acid ester compound represented by the general formula (1) is given.

[0020]

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In the formula, A ₁ represents a C ₁ -C ₆ alkyl group or an aryl group, A ₂ represents a C ₁ -C ₆ alkyl group, and A ₃ represents bis (p-alkoxyphenyl) methyl Group, 2-alkyl-2-propyl group, 2-aryl-2
-Represents a propyl group, a cyclohexyl group or a tetrahydropyranyl group, and Z represents an acid residue represented by ZOH having an acid dissociation constant (pKa) of 3 or less.

When an acid acts on this compound, the ester group is decomposed into a carboxylic acid, which further decarboxylates and then the acid (ZOH) is easily eliminated. Hereinafter, specific examples of the organic acid ester compound represented by the general formula (1) will be described.

[0023]

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Second, organic acid esters having an acetal group or a ketal group represented by the general formula (2) can be mentioned.

[0025]

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In the formula, Z is as defined above, B ₁ is a hydrogen atom, an alkyl group or an aryl group; B ₂ and B ₃ are methyl or ethyl groups or both form an ethylene or propylene group; ₄ represents a hydrogen atom or a methyl group.

In this compound, an acetal group or a ketal group is decomposed into β-aldehyde or ketone by the action of an acid, from which ZOH is easily eliminated. Hereinafter, specific examples of the organic acid ester represented by the general formula (2) will be described.

[0028]

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Third, an organic acid ester represented by the general formula (3) can be mentioned.

[0030]

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[0031] In the formula, Z is the same as defined above, D _1, D ₂ represents a hydrogen atom, an alkyl group or an aryl group of up to _{C 1 ~C 6, D 2,} D 3 until C ₁ -C ₆ Or an alkylene or substituted alkylene residue forming an alicyclic structure with the alkyl group or both.

In this compound, a hydroxyl group is eliminated by an acid catalyst to form a carbocation.
Is estimated to occur. Hereinafter, specific examples of the organic acid ester represented by the general formula (3) will be described.

[0033]

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Fourth, an organic acid ester having an epoxy ring represented by the general formula (4) can be mentioned.

[0035]

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In the formula, Z is as defined above, and E is C _1-
An alkyl group up to C ₆ or a phenyl group is shown.

When an acid acts on this compound, a cation is formed on the β-carbon with the opening of the epoxy ring,
It is estimated that organic acids are generated as a result of hydrogen transfer.
Hereinafter, specific examples of the organic acid ester represented by the general formula (4) will be described.

[0038]

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These compounds exist stably at room temperature unless an acid acts. To cause acid-catalyzed decomposition of these compounds, a certain level of acid strength is required, but it is desirable that the acid dissociation constant (pKa) is about 2 or less. If the acid dissociation constant is higher than that, that is, if the acid is weaker, the reaction of the acid multiplying agent cannot be caused.

The amount of these acid multiplying agents contained in the photosensitive composition is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.

In the present invention, other sensitizers can be used. For example, a diazo compound described below may be used in combination.

<2> Diazo-Compound-Containing Type The lithographic printing plate material of the present type comprises a support capable of producing a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond capable of being decomposed by an acid or an acid. It is provided with a photosensitive layer containing a compound which can be made insoluble in alkali in the presence thereof, an infrared absorber and a diazo compound.

In the present invention, any diazo compound can be used as long as it functions as a photosensitive compound, but it may be a low molecular weight diazo compound or a high molecular weight diazo resin, for example, an aromatic diazonium compound. A condensate of a compound and a carbonyl compound is exemplified. As this condensate, it is preferable to use one having a structure represented by the following general formula (5) or (6).

[0044]

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In the formula, R represents a hydrogen atom, an alkyl group or a phenyl group, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkoxy group or an alkyl group, and X ⁻ represents a counter anion. Y represents -NH-, -O-, or -S-. n represents an integer.

[0046]

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In the formula, A represents a condensable aromatic group, and R, R ₁ , R ₂ , R ₃ , X ⁻ , Y and n are all those used in the above formula (5). Is synonymous with

The aromatic diazonium compound serving as a structural unit of the diazo compound having the structure represented by the above general formulas (5) and (6) includes, for example, a diazonium salt as described in JP-B-49-48001. Although it can be used, diphenylamine-4-diazonium salts are particularly preferred. Diphenylamine-4-diazonium salts are derived from 4-aminodiphenylamines,
Such 4-aminodiphenylamines include 4
-Aminodiphenylamine, 4-amino-3-methoxydiphenylamine, 4-amino-2-methoxydiphenylamine, 4'-amino-2-methoxydiphenylamine, 4'-amino-4-methoxydiphenylamine, 4
-Amino-3-methyldiphenylamine, 4-amino-
3-ethoxydiphenylamine, 4-amino-3- (β
-Hydroxyethoxy) diphenylamine, 4-aminodiphenylamine-2-sulfonic acid, 4-aminodiphenylamine-2-carboxylic acid, 4-aminodiphenylamine-2'-carboxylic acid, and the like. Of these, particularly preferred are 4-aminodiphenylamine and 4-amino-3-methoxydiphenylamine.

In the general formula (6), specific examples of the aromatic compound which can be used to give the condensable aromatic group represented by A include m-chlorobenzoic acid, diphenylacetic acid, phenoxy acid and the like. Acetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4- (m-methoxyanilino ) Benzoic acid, 4- (p-methylbenzoyl)
Benzoic acid, 4- (p-methylanilino) benzoic acid, phenol, cresol, xylenol, resorcinol, 2-
Methylresorcin, methoxyphenol, ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl-4,4'-diol, 1,
2,4-benzenetriol, bisphenol A, 2,
4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, p-hydroxyacetophenone, 4,4'-dihydroxydiphenyl ether, 4,
4'-dimethoxydiphenyl ether, 4,4'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenyl sulfide, cumylphenol, chlorophenol, bromophenol, salicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid , 2,
4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-chloro-
2,6-dihydroxybenzoic acid, 4-methoxy-2,6
-Dihydroxybenzoic acid, gallic acid, phloroglysin carboxylic acid, N- (4-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) acrylamide, cinnamic acid, methyl cinnamate, ethyl cinnamate, p-hydroxycinnamic acid , Styrene, hydroxystyrene, stilbene, 4-hydroxystilbene, 4,4'-dihydroxystilbene, 4-carboxystilbene, 4,4'-
Dicarboxystilbene, diphenyl ether, diphenylamine, diphenylthioether, 4-methoxydiphenylether, 4-methoxydiphenylamine,
4-methoxydiphenylthioether and the like can be mentioned.

Among these diazo compounds contained in the photosensitive composition, a diazo compound having a carboxyl group in the molecule is particularly preferably used. Preferred examples of the diazo compound having a carboxyl group in the molecule include:
A diazo resin having a structure containing a carboxyl group in the aromatic group represented by A in the general formula (6) is exemplified. At this time, preferred specific examples of the aromatic compound that can be used to give the aromatic group represented by A include p-hydroxybenzoic acid, p-methoxybenzoic acid,
p-Hydroxycinnamic acid and phenoxyacetic acid.

The diazo resin can be prepared by a known method, for example,
Photographic Science and Engineering (Photo. Sci. Eng.) Vol. 17, p. 33 (1973); U.S. Pat. No. 2,063,631.
No. 2,679,498, JP-B-49-
No. 48001, aromatic diazonium salt in sulfuric acid, phosphoric acid or hydrochloric acid, an aromatic compound providing an aromatic group represented by A of the above general formula (6) if necessary, and an active carbonyl compound For example, by polycondensing paraformaldehyde, acetaldehyde, benzaldehyde, acetone, acetophenone, or the like.

The aromatic compound, aromatic diazo compound and active carbonyl compound which give an aromatic group represented by A in the general formula (6) can be freely combined with each other. It is also possible to mix and condense. In addition, at the time of the condensation, the number of moles of the charged aromatic compound giving an aromatic group represented by A is preferably 0.1 to 10 times, more preferably 0.1 to 10 times the number of moles of the aromatic diazonium compound. Is 0.2 to 2 times, more preferably 0.2 to 1 time. In this case, the active carbonyl compound is usually 0.5 to 1.5 times, preferably 0.5 to 1.5 times the total number of moles of the aromatic compound giving the aromatic group represented by A and the aromatic diazonium compound. The diazo resin is obtained by charging the mixture at 0.6 to 1.2 times and reacting at a low temperature for a short time, for example, about 3 hours.

The means for synthesizing a diazo compound having a carboxyl group in the molecule which can be more preferably used in the present invention is optional, but typical means include:
(A) a polycondensation reaction of an aromatic diazonium salt, an aromatic carboxylic acid, and an active carbonyl compound, (B) a polycondensation reaction of an aromatic diazonium salt having a carboxyl group and an active carbonyl compound, and (C) an aromatic diazonium salt. There are three types of polycondensation reaction of an active carbonyl compound having a carboxyl group. Among these methods, the method (A) is preferable from the viewpoint of the synthesis technique and the availability of synthesis raw materials.

The counter anion of the diazo compound is preferably an anion which forms a salt with the diazo compound stably and makes the compound soluble in an organic solvent. Examples of the acid forming such an anion include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and organic sulfonic acids.Typical examples include methanesulfonic acid, chloroethanesulfonic acid, Dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, anthraquinonesulfonic acid, naphthylsulfonic acid, aliphatic sulfonic acid such as alkyl-substituted naphthylsulfonic acid and aromatic sulfonic acid, hexafluorophosphoric acid,
Examples thereof include halogenated Lewis acids such as tetrafluoroboric acid, and perhalogen acids such as perchloric acid and periodic acid. However, it is not limited to this. Of these, hexafluorophosphoric acid and tetrafluoroboric acid are particularly preferred.

In the present invention, the molecular weight of the diazo compound used is not particularly limited. For example, the molecular weight of the above diazo resin can be set to any value by changing the molar ratio of each monomer and the condensation conditions. In general, in the present invention, those having a molecular weight of about 400 to 10,000 can be used effectively, and those having a molecular weight of about 800 to 5,000 are more suitable.

The amount of these diazo compounds contained in the photosensitive composition is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.

The following is an example of the synthesis of a diazo compound.

(Synthesis of diazo compound 1) 4-diazodiphenylamine sulfate 1 was added to 45.0 g of ice-cooled concentrated sulfuric acid.
4.65 g (0.05 mol) is stirred and dissolved while taking care that the liquid temperature does not exceed 5 ° C. Next, 1.05 g (0.035 mol) of paraformaldehyde is slowly added over 1 hour with stirring to carry out a condensation reaction. At this time, care is taken so that the temperature of the reaction solution does not exceed 5 ° C. After the addition of paraformaldehyde, stirring is continued at 5 ° C. or lower for 30 minutes. After the completion of the reaction, the reaction solution is slowly poured into 400 ml of ethanol cooled to 0 ° C. to produce a precipitate. At this time, care is taken that the liquid temperature does not exceed 40 ° C. The precipitate was collected by suction filtration and washed with 100 ml of ethanol to obtain Reaction Intermediate 1a (diazo resin sulfate). The reaction intermediate 1a taken out was dissolved in 100 ml of water, and then 6.81 g (0.05 mol of zinc chloride) dissolved in 30 ml of water.
When l) is added, a precipitate is formed again. The precipitate was collected by suction filtration to obtain Reaction Intermediate 1b (diazo resin zinc chloride double salt).

The reaction intermediate 1b taken out was mixed with 200 ml of water.
Then, 8.15 g (0.05 mol) of ammonium hexafluorophosphate dissolved in 40 ml of water is added to generate a precipitate. The precipitate was collected by suction filtration, washed with 100 ml of ethanol, and dried at 30 ° C. for 3 days to obtain 11.1 g of diazo compound 1.

Molecular weight 4-diazodiphenylamine sulfate 293 Paraformaldehyde 30.03 Zinc chloride 136.3 Ammonium hexafluorophosphate 162.9 DR resin unit 353 (Synthesis of diazo compound 2) 200 g of ice-cooled concentrated sulfuric acid
In addition, p-hydroxybenzoic acid 12.7g (0.092m
ol) and 40.5 g of 4-diazodiphenylamine sulfate
(0.138 mol) is stirred and dissolved while taking care that the liquid temperature does not exceed 5 ° C. Then, 6.22 g (0.207 mol) of paraformaldehyde is slowly added over 1 hour with stirring to carry out a condensation reaction. At this time, care is taken so that the temperature of the reaction solution does not exceed 5 ° C. After the addition of paraformaldehyde, stirring is continued at 5 ° C. or lower for 30 minutes. After completion of the reaction, the reaction solution was cooled to 0 ° C. with ethanol 1
When slowly poured into 600 ml, a precipitate is formed.
At this time, care is taken that the liquid temperature does not exceed 40 ° C. The precipitate was collected by suction filtration, and washed with 300 ml of ethanol to obtain a reaction intermediate 1a (diazo resin sulfate). After dissolving the reaction intermediate 1a taken out in 240 ml of water,
19.04 g of zinc chloride dissolved in 0.1 ml (0.14 mol
When l) is added, a precipitate is formed again. The precipitate was collected by suction filtration to obtain Reaction Intermediate 1b (diazo resin zinc chloride double salt). The taken out reaction intermediate 1b is put into water 1000m
Then, 24.8 g (0.15 mol) of ammonium hexafluorophosphate dissolved in 180 ml of water is added, and a precipitate is formed. The precipitate is collected by suction filtration,
After washing with 300 ml of ethanol, it was dried at 30 ° C. for 3 days to obtain 32.4 g of diazo compound 2.

In the present invention, other sensitizers can be used. For example, the acid sensitizer described above may be used in combination.

Next, the photosensitive layer composition for forming the photosensitive layer will be described.

(Compound capable of generating an acid upon irradiation with actinic rays) Examples of the compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as a photoacid generator) include various known compounds and mixtures. For example, diazonium, phosphonium,
BF ₄ ⁻ , PF ₆ ⁻ , S of sulfonium and iodonium
Salts such as bF ₆ ⁻ , SiF ₆ ²⁻ , and ClO ₄ ⁻
2158, an alkylonium salt, an organic halogen compound, orthoquinone-diazidosulfonyl chloride,
And an organometallic / organohalogen compound is also an actinic ray-sensitive component that forms or separates an acid upon irradiation with actinic ray,
It can be used as a photoacid generator in the present invention. In principle, all organic halogen compounds known as free radical-forming photoinitiators are compounds which form hydrohalic acid and can be used as photoacid generators in the present invention.

Examples of the compounds forming the above-mentioned hydrohalic acid include US Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent Publication. No. 2,243,621, and compounds capable of generating an acid by photolysis described in, for example, West German Patent Publication No. 2,610,842 can also be used. Also, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209,
No. 134410, an acid generator capable of forming an acid polymer by ultraviolet rays, for example, a compound having two oxysulfonyl groups and two oxycarbonyl groups, and an acid generator described in JP-A-4-19666. Specifically, tetrakis-
Aryl halides such as 1,2,4,5- (polyhalomethyl) benzene, tris (polyhalomethyl) benzene,
The polymer sulfonium salt containing silyl ether and the alkyl halide disclosed in JP-A-6-342209 are disclosed in JP-A-9-342209.
Oxime sulfonate compounds of JP-A-96900 and JP-A-6-67433, halogenated sulfolane derivatives of JP-A-4-338557, JP-A-6-236024, JP-A-6-214391, JP-A-6-214392,
Sulfonic esters of N-hydroxyimide compounds, diazo compounds or diazo resins described in JP-A-7-244378 can be used.

In the present invention, a photoacid generator is preferred from the viewpoints of sensitivity of an organic halogen compound for image formation by infrared exposure and storage stability when used as an image forming material. As the organic halogen compound, a triazine having a halogen-substituted alkyl group and an oxadiazole having a halogen-substituted alkyl group are preferable, and an s-triazine having a halogen-substituted alkyl group is particularly preferable. Specific examples of oxadiazoles having a halogen-substituted alkyl group include JP-A-54-74728, JP-A-55-24113, JP-A-55-77742, JP-A-60-3626 and JP-A-60-3626. 2-halomethyl-1,3,4-oxadiazole compounds described in JP-A-60-138439 and oxadiazole compounds described in JP-A-4-46344. 2-halomethyl-
Preferred compound examples of the 1,3,4-oxadiazole-based photoacid generator are shown below.

[0066]

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S- having the halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (9) is preferable.

[0068]

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In the general formula (9), R represents an alkyl group,
A halogen-substituted alkyl group, a phenylvinylene group or an aryl group (for example, a phenyl group, a naphthyl group or the like) which may be substituted with an alkoxy group, or a substituted product thereof;
X ₃ represents a halogen atom. S represented by the general formula (9)
-Examples of compounds of the triazine-based photoacid generator are shown below.

[0070]

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[0071]

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[0072]

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The s-triazine photoacid generator is also disclosed in
Specific examples described in JP-A-47737, JP-A-9-90633, and JP-A-4-226454 can also be used.

In the present invention, the photoacid generator comprises the following 1
It is preferable to correspond to any one of the above.

1. 1. having an alkali-soluble site; 2. a bromomethylaryl ketone derivative; It is a trichloroacetylamino group-containing aromatic compound.

Examples of the compound having an alkali-soluble moiety include an ester having a combination selected from the following, a compound having two or more hydroxyl groups and an alkylsulfonic acid, a compound having two or more phenolic hydroxyl groups and an alkylsulfonic acid, An anthracene derivative having two or more hydroxyl groups and a sulfonic acid can be given.

[0077] Acid generators comprising an ester of a compound having two or more hydroxyl groups and an alkyl sulfonic acid include esters of an alcoholic hydroxyl group such as ethylene glycol, propylene glycol, glycerin, and 1,2,4-butanetriol with an alkyl sulfonic acid. Is mentioned. Alkyl group of the alkyl sulfonic acid is C _n H2
Those where _{n + 1} and n = 1 to 4 are effective. It is also effective to substitute a part or all of the hydrogen in the alkyl group with a halogen having a high electronegativity such as fluorine or chlorine. The alkyl sulfonic acid ester used for the photoacid generator does not need to convert all the hydroxyl groups of the compound containing two or more alcoholic hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

[0078] Examples of the photoacid generator comprising an ester of a compound having two or more phenolic hydroxyl groups and an alkylsulfonic acid include catechol, resorcin, hydroquinone, pyrogallol, oxyhydroquinone, phloroglucin, trihydrobenzophenone, tetrahydrobenzophenone, and gallic acid ester. And an ester of a phenolic hydroxyl group with an alkylsulfonic acid. The alkyl group of the alkylsulfonic acid is the same as described above. The alkyl sulfonic acid ester used for the photoacid generator does not need to convert all the hydroxyl groups of the compound containing two or more alcoholic hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

[0079] Examples of the photoacid generator comprising an ester of an anthracene derivative having two or more hydroxyl groups and a sulfonic acid include, for example, esters of a hydroxyl group of dihydroxyanthracene, trihydroxyanthracene, and tetrahydroxyanthracene with a sulfonic acid. Examples of the sulfonic acid include alkylsulfonic acid, arylsulfonic acid, and 1,2-naphthoquinonediazidosulfonic acid. The alkyl of the alkyl sulfonic acid is the same as described above. The sulfonic acid ester used for the photoacid generator does not need to convert all of the hydroxyl groups of the compound containing two or more hydroxyl groups into esters, and the hydroxyl groups may be left. By doing so, it is possible to control the solubility in an alkaline aqueous solution.

As the bromomethylarylketone derivative, bromomethylarylketone or dibromomethylarylketone is preferable. For example, 2-bromoacetylnaphthalene, 2-bromoacetyl-6,7-dimethoxynaphthalene, 2-bromoacetylnaphthalene, 2-dibromoacetyl-6,7-dimethoxynaphthalene, 1-
Hydroxy-4-bromo-2-bromoacetylnaphthalene, 1-hydroxy-4-bromo-2-dibromoacetylnaphthalene, 2-hydroxy-1-bromoacetylnaphthalene, 1,4-bis (bromoacetyl) benzene,
4,4'-bis (bromoacetyl) biphenyl, 1,
3,5-tris (bromoacetyl) benzene, 1,3
5-tris (dibromoacetyl) benzene and the like, and these can be used alone or in combination of two or more.

Further, as the aromatic compound containing a trichloroacetylamino group, those having the following structures are more preferable.

[0082]

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In the formula, R _{1 to} R ₅ represent hydrogen, an alkyl or alkoxy group having 4 or less carbon atoms, a halogen atom, a phenylamino group, a phenoxy group, a benzyl group, a benzoyl group, an acetyl group, and a trichloroacetylamino group. , R _1-
R ₅ may be the same or different. Specifically, for example, 4-phenoxytrichloroacetanilide,
4-methoxytrichloroacetanilide, 2,3-dimethoxytrichloroacetanilide, 4-methoxy-2-
Chlorotrichloroacetanilide, 3-acetyltrichloroacetanilide, 4-phenyltrichloroacetanilide, 2,3,4-trifluorotrichloroacetanilide, 2,4,5-trimethyltrichloroacetanilide, 2,4,6-tribromotrichloroacetanilide, 2, 4,6-trimethyltrichloroacetanilide, 2,4-dichlorotrichloroacetanilide, 2,
4, -dimethoxytrichloroacetanilide, 2,5-
Dichlorotrichloroacetanilide, 2,5-dimethoxytrichloroacetanilide, 2,6-dimethyltrichloroacetanilide, 2-ethyltrichloroacetanilide, 2-fluorotrichloroacetanilide, 2-methyltrichloroacetanilide, 2-methyl-6-ethyltrichloroacetanilide, 2- Phenoxyacetanilide, 2-propyltrichloroacetanilide, 3,
4-dichlorotrichloroacetanilide, 3,4-dimethoxytrichloroacetanilide, 3,4-dimethyltrichloroacetanilide, 4-butylacetanilide,
4-ethylacetanilide, 4-fluoroacetanilide, 4-iodoacetanilide, 4-propylacetanilide, 2,3,4,5,6-pentafluoroacetanilide, 4-propoxyacetanilide, 4-acetylacetanilide and the like, In particular, since they have high thermal stability and do not inhibit the solubility of the acid crosslinking agent in an aqueous alkali solution, they can be suitable photoacid generators.

In the present invention, one or more photoacid generators can be used alone or in combination. The content of the photoacid generator can be varied widely depending on its chemical properties and the photosensitive composition or its physical properties. The range of about 0.1 to about 20% by weight, and preferably 0.2 to 10% by weight, based on the total weight of the solid content of the photosensitive layer when the composition is in a dry state or as an image forming material is suitable. Range.

(Compound having at least one bond decomposable by acid) The compound having at least one bond decomposable by acid (hereinafter referred to as acid-decomposable compound) is specifically described in JP-A-48-89003. No. 51-120714
No. 53-133429, No. 55-12959,
Compounds having a C--O--C bond described in JP-A-55-126236 and JP-A-56-17345;
Compounds having a Si--O--C bond described in JP-A-37549 and JP-A-60-112446;
And other acid-decomposable compounds described in JP-A Nos. 625-625 and 60-10247.
Compounds having a Si-N bond described in JP-A-222246, carbonates described in JP-A-62-251743, orthotitanates described in JP-A-62-280841, 62-280
No. 842, orthosilicates and ketals described in JP-A-63-10153, compounds having a CS bond described in JP-A-62-244038, A compound having a -OC (= O)-bond of No. 231442 or the like can be used.

Of the above, compounds having a C—O—C bond, compounds having a Si—O—C bond, orthocarbonates, acetals and silyl ethers are preferred.
Among them, the organic polymer compounds described in JP-A-53-133429, which have a repeating acetal moiety in the main chain and whose solubility in a developer is increased by the action of an acid, and JP-A-63-133429. No. 10153, JP-A-9-54
The compounds described in No. 437 are particularly preferred.

Particularly preferred specific examples of the acid-decomposable compound in the present invention include a compound represented by the following general formula (7).

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In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and any two of R _{1 to} R ₄ may combine to form a ring; It may have an ether bond, and R _{1 to} R ₄ may be the same or different. Further, each substituent may be introduced.

In the general formula (7), examples of the alkyl group represented by R ₁ and R ₂ include a lower alkyl group having 1 to 8 carbon atoms, and examples of the aryl group include a substituted or unsubstituted phenyl group. Can be When R ₁ and R ₂ combine to form a ring to form a cycloalkyl group, examples of the cycloalkyl group include a 4- to 8-membered cycloalkyl ring, and a cyclohexyl group is preferable. Examples of the alkyl group represented by R ₃ and R ₄ include a lower alkyl group having 1 to 4 carbon atoms, and examples of the aryl group include a substituted or unsubstituted phenyl group. These preferably have an ether bond, and particularly preferably an ethyleneoxy group. Note that R _{1 to} R
₄ may be the same or different from each other. Further, a substituent or a substituent atom may be introduced, and the substituent may be an acidic group or a basic group, and the substituent atom may be a halogen atom.

Examples of the acidic group include those having a hydroxyl group (phenol, cresol, xylenol, etc.) and those having a carboxyl group (benzoic acid, methylbenzoic acid, butylbenzoic acid, salicylic acid, gallic acid, etc.). However, the present invention is not limited to this. Examples of the basic group include, for example, those having an amino group (amine,
Aniline and the like), but are not limited thereto.

The specific compound represented by the general formula (7) includes the following acid-decomposable compound A.

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Another preferred acid-decomposable compound is a compound having a repeating structural unit represented by the general formula (8).

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In the formula, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and have the same meaning as R ₁ and R _{2 in} the general formula (7). Also, n and n '
Represents an integer of 1 to 6, preferably 1 to 3, and m
Represents an integer of 1 to 80, preferably 10 to 20.

As a specific compound represented by the general formula (8), the following acid-decomposable compound B can be mentioned.

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The method for synthesizing the acid-decomposable compounds A and B is described below.

(Synthesis of acid-decomposable compound A) 0.5 mol of cyclohexanone, 1.0 mol of phenyl cellosolve and p-
80 mg of toluenesulfonic acid was reacted at 100 ° C. for 1 hour while stirring, then the temperature was gradually raised to 150 ° C., and the reaction was further performed at 150 ° C. for 4 hours. Methanol generated by the reaction was distilled off during this period. After cooling, 500 ml of tetrahydrofuran and 2.5 g of anhydrous potassium carbonate were added, followed by stirring and filtration. The solvent was distilled off from the filtrate under reduced pressure, and the low-boiling components were further distilled off at 150 ° C. under a high vacuum to obtain a viscous oily acid-decomposed compound A.

(Synthesis of acid-decomposable compound B) 1.0 mol of cyclohexanone, 1.0 mol of ethylene glycol and p-
80 mg of toluenesulfonic acid was reacted at 100 ° C. for 1 hour while stirring, then the temperature was gradually raised to 150 ° C., and the reaction was further performed at 150 ° C. for 4 hours. Methanol generated by the reaction was distilled off during this period. After cooling, 500 ml of tetrahydrofuran and 2.5 g of anhydrous potassium carbonate were added, followed by stirring and filtration. The solvent was distilled off from the filtrate under reduced pressure, and the low-boiling component was further distilled off at 150 ° C. under a high vacuum to obtain a viscous oily acid-decomposed compound B.

(Compound which can be insolubilized in alkali in the presence of acid) Compounds which can be insolubilized in alkali in the presence of acid (hereinafter referred to as acid insolubilizing agents) include those which are insolubilized in the presence of acid and soluble in alkali. And the like. The degree to which the solubility in alkali can be reduced may be such that the resin is changed to physical properties showing complete alkali insolubility by finally insolubilizing, such as crosslinking with an alkali-soluble resin. What was originally alkali-soluble by the action of the acid insolubilizing agent shows insolubility in an alkaline solution used as a developer and remains on the printing plate. Examples of the acid insolubilizer include a methylol group or a derivative of a methylol group, a melamine resin, a furan resin, an isocyanate, a blocked-isocyanate (an isocyanate having a protective group), and a methylol group or an acetylated methylol group. Preferred are compounds and resole resins.

The acid insolubilizing agent further includes a silanol compound, a compound containing a carboxylic acid or a derivative thereof, a hydroxy group-containing compound, a compound having a cationically polymerizable double bond,
Secondary or tertiary alcohol having an aromatic group, an alkali-soluble polymer having an aromatic having a methylol group, an alkoxymethyl group or an acetoxymethyl group in a molecule, an aminoplast, and a compound represented by the following general formula (p) Compounds, alicyclic alcohols and / or heterocyclic alcohols can be mentioned. Hereinafter, description will be made in order.

The silanol compound is a compound having one or more hydroxyl groups bonded to silicon atoms on average per silicon atom. Here the average is
For example, even if there is one silicon atom to which no hydroxyl group is bonded in the compound, the same effect can be obtained if there is one silicon atom to which two hydroxyl groups are bonded. Such silanol compounds include, for example, diphenylsilanediol, triphenylsilanol, cis- (1,3,5,7-tetrahydroxy)-
1,3,5,7-tetraphenylcyclotetrasiloxane and the like can be used.

The amount of the silanol compound is 5 to 70% by weight.
Is preferably within the range.

Compounds containing a carboxylic acid or a carboxylic acid derivative include aromatic carboxylic acids such as cinnamic acid, benzoic acid, tolylacetic acid, toluic acid, and isophthalic acid, and aromatic compounds such as dimethyl isophthalate and di-t-butyl isophthalate. And acid anhydrides such as aliphatic esters, glutaric anhydride, succinic anhydride, and benzoic anhydride; and copolymers such as styrene-maleic anhydride copolymer and styrene-methacrylic acid copolymer.

As the compound having a hydroxyl group,
Polyhydric alcohols such as glycerin, poly p-hydroxystyrene, p-hydroxystyrene / styrene copolymer,
High molecular compounds such as novolak resins are exemplified.

The compound having a carboxylic acid or a derivative thereof and the compound having a hydroxyl group are preferably used in combination, and the composition ratio thereof is preferably in the range of 1:30 to 30 to 1 in terms of equivalent ratio. One of the compound having a hydroxyl group and the compound having a carboxylic acid or a derivative thereof may be a high molecular compound. When the compound having a hydroxyl group is a polymer compound, it is preferable to use a carboxylic acid or a derivative thereof in an amount of 1 to 50 in a weight ratio to the polymer compound 100. When the compound having a carboxylic acid or a derivative thereof is a polymer compound, it is preferable to use a compound having a hydroxyl group with respect to the polymer compound 100 in an amount of 1 to 20 in a weight ratio.

From the viewpoint of film-forming properties, it is preferable that at least one of the compound having a carboxylic acid or a derivative thereof and the compound having a hydroxyl group is a polymer compound. However, even if both are low molecular weight, it is sufficient that the coating film can be formed by a method such as mixing a high molecular compound. Preferred examples of the high molecular compound include alkali-soluble polymers.

A high molecular compound having both a compound having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative can be used. Examples of the polymer compound include p-hydroxystyrene having a hydroxyl group and a carboxylic acid or a carboxylic acid derivative, such as methacrylic acid ester such as methyl methacrylate, acrylic acid ester such as methyl acrylate, maleic anhydride, methacrylic acid, and acrylic acid. And the like.

The weight average molecular weight of these high molecular compounds is desirably in the range of 1,000 to 50,000. If the molecular weight is less than 1,000, sufficient heat resistance and coating properties cannot be obtained. On the other hand, when the molecular weight exceeds 50,000, the solubility in an aqueous alkali solution is not sufficient, and pattern deformation due to swelling is observed, so that high resolution cannot be obtained.

The amount of the compound having a carboxylic acid or a derivative thereof and the compound having a hydroxyl group are 5 to 5
It is preferably in the range of 0% by weight.

Examples of the compound having a cationically polymerizable double bond include p-diisopropenylbenzene, m-diisopropenylbenzene, diphenylethylene, indenone,
Acenaphthene, 2-norbornene, 2,5-norbornadiene, 2,3-benzofuran, indole, 5-methoxyindole, 5-methoxy-2-methylindole, N-vinyl-2-pyrrolidone, N-vinylcarbazole At least one compound selected from the group can be mentioned. The amount of the compound having a cationic double bond is preferably in the range of 5 to 50% by weight.

Examples of the secondary or tertiary alcohol having an aromatic group include biphenyl derivatives, naphthalene derivatives and triphenyl derivatives, and are specifically represented by the following general formulas (a) to (d). Compounds.

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In the general formulas (a) to (d), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom,
X represents a methyl group or an ethyl group, X represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and Y represents -SO _{2
-, - CH 2 -, -} S -, - C (CH 3) 2 - represents, n
Represents 1 or 2.

As specific compounds, for example, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl,
3,3'-bis (α-hydroxyisopropyl) biphenyl, 2,4,2 ', 4'-tetra (α-hydroxyisopropyl) biphenyl, 3,5,3', 5'-tetra (α-hydroxyisopropyl) Biphenyl, 4,4 '
-Bis (α-hydroxyisopropyl) biphenyl sulfone, 3,3′-bis (α-hydroxyisopropyl)
Biphenyl sulfone, 4,4'-bis (α-hydroxyisopropyl) biphenylmethane, 3,3'-bis (α
-Hydroxyisopropyl) biphenylmethane, 4,
4'-bis (α-hydroxyisopropyl) biphenyl sulfide, 3,3'-bis (α-hydroxyisopropyl) biphenyl sulfide, 2,2-bis (4-α-
Hydroxyisopropylphenyl) propane, 2,2-
And bis (3-α-hydroxyisopropylphenyl) propane. The naphthalene derivative is 1,5-bis (1
-Hydroxypropyl) naphthalene, 2,6-bis (α
-Hydroxypropyl) naphthalene and the like. Triphenyl derivatives include tris (4-α-hydroxyisopropylphenyl) methane, tris (3-α-hydroxyisopropylphenyl) methane, 1,1,1-tris (4-
α-hydroxyisopropylphenyl) ethane, 1,
1,1-tris (3-α-hydroxyisopropylphenyl) ethane and the like.

As the secondary or tertiary alcohol having an aromatic group, compounds represented by the following formulas (e) to (g) can be further exemplified.

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In the general formula (e), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, a halogen atom or a methoxy group, and R ₃ represents a hydrogen atom, a phenyl group or a cyclopropyl group. . In the general formula (f), R
₄ and R ₅ may be the same or different and each represents a hydrogen atom or a phenyl group. In the general formula (g), A represents an alkyl group having 4 or less carbon atoms or a methylol group. Secondary or tertiary alcohols having a hydroxyl group at the carbon directly bonded to the aromatic ring include phenylmethanol derivatives, alicyclic alcohols having an aromatic ring, and the like.

The phenylmethanol derivatives include:
For example, diphenylmethanol, 4,4'-difluorodiphenylmethanol, 4,4'-dichloro-diphenylmethanol, 4,4'-dimethyl-diphenylmethanol, 4,4'-dimethoxydiphenylmethanol, triphenylmethanol, α- (4 -Pyridyl) -benzhydrol, benzylphenylmethanol, 1,1-diphenylethanol, cyclopropyldiphenylmethanol, 1-phenylethyl alcohol, 2-phenyl-2
-Propanol, 2-phenyl-2-butanol, 1-
Phenyl-1-butanol, 2-phenyl-3-butyn-2-ol, 1-phenyl-1-propanol, 1,
2-diphenylethylene glycol, tetraphenylethylene glycol, 2,3-diphenyl-2,3-butanediol, α-naphtholbenzein, α, α′-dihydroxy-p-diisopropylbenzene, α, α′-
Dihydroxy-m-diisopropylbenzene and the like.

Examples of the alicyclic alcohol having an aromatic ring include 1-indanol, 2-bromoindanol, chromanol, 9-fluorenol, and 9-hydroxy-3.
-Fluorene, 9-hydroxyxanthene, 1-acenaphthenol, 9-hydroxy-3-nitrofluorene,
Thiochroman-4-ol, 9-phenylxanthene-
9-ol, 1,5-dihydroxy-1,2,3,4-
Tetrahydronaphthalene, dibenzosuberenol, dibenzosuberol and the like can be mentioned.

Further, in addition to the above, 1- (9-anthryl) ethanol, 2,2,2
Examples thereof include 2-trifluoro-1- (9-anthryl) ethanol and 1-naphthylethanol.

Examples of the alkali-soluble polymer having an aromatic ring having a methylol group, an alkoxymethyl group or an acetoxymethyl group in the molecule include one or two hydrogen atoms on the aromatic ring of the compound represented by the following general formula (h). Polymers having the excluded group in the molecule are exemplified.

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In the general formula (h), X represents a methylol group, an alkoxymethyl group having 1 to 5 carbon atoms or an acetoxymethyl group. Y represents an alkyl group, a hydroxyl group, a halogen atom, a hydrogen atom, or an alkoxy group.

As the alkali-soluble polymer, a polymer compound having a repeating unit represented by the following general formula (i) or (j) is preferable.

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In the general formulas (i) and (j), R ₁ represents an alkyl group, a hydrogen atom, a halogen atom or a cyano group, and L represents a single bond, —O—, —O—CO—, —CONR _{3
-, - CONR 3 CO -,} - CONR 3 SO 2 -, - NR 3
_{-, - NR 3 CO -,} - NR 3 SO 2 -, - SO 2 -, - S
O ₂ NR ₃ — or —SO ₂ NR ₃ CO— (R ₃ is a hydrogen atom,
Alkyl group, aralkyl group or aromatic ring group). X and Y have the same meanings as X and Y in formula (h).

The repeating unit represented by the above general formula (i) or (j) includes vinyl benzyl alcohol, α-methyl vinyl benzyl alcohol, vinyl benzyl acetate, α-methyl vinyl benzyl acetate, p-methoxy styrene, It is preferable to copolymerize with a monomer such as methylolphenyl methacrylamide.

The aminoplast is preferably a compound represented by the following general formula (k).

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In the general formula (k), Z represents -NRR 'or a phenyl group. _{R, R ', R 10 ~R} 13 each represents a hydrogen atom, -CH ₂ OH, -CH ₂ OR _a or -CO-OR _a. R _a represents an alkyl group.

The melamine or benzoguanamine represented by the general formula (k) can be easily obtained as a commercial product, and their methylols can be obtained by condensation of melamine or benzoguanamine with formalin. Ethers can be obtained by modifying a methylol compound with various alcohols by a known method. As the alkyl group represented by _Ra in the general formula (k), an alkyl group having 1 to 4 carbon atoms which may be linear or branched is preferable.

Specific examples of the compound represented by the general formula (k) include, but are not limited to, the following.

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As the aminoplast, the following general formula (1)
A melamine resin in which a plurality of triazine nuclei are bonded through a bond represented by the following general formula (m), and a compound represented by the following general formula (n) or (o). can do.

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In the general formulas (1) to (o), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The compound represented by the general formula (p) is as follows.

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In the formula, R represents a hydrogen atom, an alkyl group having 3 or less carbon atoms, an aryl group or a tolyl group, and R ₁ , R ₂ , R
₃ and R ₄ each represent a hydrogen atom, an alkyl group having 3 or less carbon atoms, or an alkoxy group having 3 or less carbon atoms.

As the compound represented by the general formula (p), o
-Acetylbenzoic acid, o-aldehydebenzoic acid, o-benzoylbenzoic acid, o-toluoylbenzoic acid, and o-acetoxybenzoic acid are preferably used.

The content of the compound represented by formula (p) in the photosensitive layer is suitably in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

As the alicyclic alcohol, for example, 2-
Adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol, 2-propyl-2-adamantanol, 2-butyl-2-adamantanol, exo-norborneol, endo-norborneol, borneol , DL-isoborneol,
Terpinen-4-ol, S-cis-verbenol, isopinocanphenol, pinanediol and the like.

The heterocyclic alcohol includes, for example, 1,
4-dioxane-2,3-diol, 5-methyl-1,
4-dioxane-2,3-diol, 5,6-dimethyl-1,4-dioxane-2,3-diol, DL-ex
o-Hydroxytropinone, 4-hydroxy-4-phenylpiperidine, 3-quinuclidinol, 4-chromanol, thiochroman-4-ol, DL-mavalonic acid lactone and the like. The heterocyclic alcohol preferably contains O or S in the heterocyclic ring.

The alcohol includes an alicyclic alcohol,
A secondary or tertiary alcohol may be further used in addition to the heterocyclic alcohol. The content of the alicyclic or heterocyclic alcohol is suitably from 5 to 50% by weight, and preferably from 10 to 30% by weight.

(Infrared absorber) As the infrared absorber used in the present invention, those capable of imparting a function of sensitizing the photosensitive layer to an absorption wavelength of 700 to 2000 nm are preferable. External absorption dyes, carbon black, magnetic powder, and the like can be used. A particularly preferred infrared absorbing agent is an infrared absorbing dye having an absorption peak at 700 to 850 nm and a molar absorption coefficient ε at the peak of 10 ⁵ or more.

Examples of the infrared absorbing dye include cyanine dyes, squarium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, thiopyrylium dyes, and dithiol metal dyes. Examples include complex dyes, anthraquinone dyes, indoaniline metal complex dyes, and intermolecular CT dyes. Examples of the infrared absorbing dye include JP-A-63-139191 and JP-A-64-33547.
No., JP-A-1-160683 and 1-280750
Nos. 1-293342, 2-2074, 3-
No. 26593, No. 3-30991, No. 3-34891
No. 3-36093, No. 3-36094, No. 3-
No. 36095, No. 3-42281, No. 3-10347
No. 6 and the like.

In the present invention, a cyanine dye represented by the following general formula (10) or (11) is particularly preferred as the infrared absorber.

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In the formula, Z ₁ and Z ₂ each represent a sulfur atom, a selenium atom or an oxygen atom, and X ₁ and X ₂ each form an optionally substituted benzo-fused ring or naphtho-fused ring. And R ₃ and R ₄ each represent a substituent, and one of R ₃ and R ₄ has an anionic dissociable group. R ₅ , R ₆ , R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a halogen atom. L represents a chain of conjugated bonds having 5 to 13 carbon atoms.

The cyanine dyes represented by formula (10) or (11) include those in which formula (10) or (11) forms a cation and has a counter anion. In this case, as the counter ^{anion, Cl -, Br -, ClO} 4 -,
BF ₄ ⁻ , alkylboron such as t-butyltriphenylboron, and the like.

In the general formulas (10) and (11), L
When a laser emitting infrared light is used as a light source for image exposure, the number of carbon atoms (n) in the chain of conjugated bonds represented by is preferably selected from an effective value according to the transmission wavelength of the laser. . For example, an emission wavelength of 1060 nm
When a YAG laser is used, n is preferably 9 to 13. The conjugate bond may have any substituent, and the conjugate bond may form a ring with a plurality of substituents. Further, the ring represented by X ₁ and the ring represented by X ₂ can have an arbitrary substituent. Halogen atom as the substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, (the M hydrogen atom or an alkali metal atom) -SO ₃ M and -COOM is a group selected from the preferred . R ₃ and R ₄ are each an arbitrary substituent, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;-((C
_{H 2) n -O-) k -} (CH 2) m OR (n and m are each 1
An integer from 1 to 3, k is 0 or 1, and R represents an alkyl group having 1 to 5 carbon atoms. ); One of R ₃ and R ₄ is —R—SO ₃
M on the other hand is -R-SO ₃ ^- (R is an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom); or the other one is in -R-COOM of R ₃ and R ₄ -R -COO ^- (R
Represents an alkyl group having 1 to 5 carbon atoms, and M represents an alkali metal atom. ). R ₃ and R ₄ are, in terms of sensitivity and developability, R ₃ and one is above R ₄ -R-SO ₃ ^- or -R
—COO ⁻ , the other being —R—SO ₃ M or —R-COO
M is preferred.

The cyanine dye represented by formula (10) or (11) has an absorption peak at 750 to 900 nm when a semiconductor laser is used as a light source for image exposure, and at 900 to 1200 nm when a YAG laser is used. And those having a molar extinction coefficient of ε> 1 × 10 ⁵ are preferred.

Typical examples of the infrared absorbing agent preferably used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

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These dyes can be synthesized by known methods, but the following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-20, Mitsui Toatsu: KIR103, SIR10
3 (phthalocyanine); KIR101, SIR114
(Anthraquinone type); PA1001, PA1005
PA1006, SIR128 (metal complex type), Dainippon Ink & Chemicals: Fastogen blue 8120, Midori Kagaku: MIR-101, 1011, 1021 and the like. In addition, it is also commercially available from various companies such as Nippon Kogaku Dye, Sumitomo Chemical, Fuji Photo Film and the like.

In the present invention, the amount of the infrared absorber added is
A range of 0.5 to 10% by weight is preferred. The added amount is 10
If the amount is more than 0.5% by weight, the developability of the non-image portion (exposed portion) decreases, and if the amount is less than 0.5% by weight, the development resistance of the image portion decreases.

The lithographic printing plate material of the present invention can significantly improve the printing durability when used as a lithographic printing plate by having a pigment. Examples of the pigment include known organic and inorganic pigments, and the pigments described in “Coloring Material Engineering Handbook” by Asakura Shoten and “Pigment Handbook” by Seibundo Shinkosha can be used without any particular limitation. Further, in order to obtain visible image after development, the pigment is preferably colored, and more preferably a high density is obtained. In that respect, it is preferable that the pigment is selected from phthalocyanine and carbon black not only to improve the printing durability but also to obtain a visible image after development.

(Binder) The lithographic printing plate material of the invention preferably contains an alkali-soluble resin.
Examples of the alkali-soluble resin include a novolak resin, a polymer having a hydroxystyrene unit, a polymer having a structural unit represented by the following general formula (12), and other known acrylic resins.

Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensate resin described in JP-A-55-57841, and JP-A-55-57841. And a copolycondensate resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP 127553.

Examples of the polymer having a hydroxystyrene unit include polyhydroxystyrene and a hydroxystyrene copolymer described in JP-B-52-41050.

The polymer having a structural unit represented by the general formula (12) may be a homopolymer having a repeating structure composed of only the structural unit or an unsaturated dimer of the structural unit and another vinyl monomer. It is a copolymer in which one or more structural units having a structure in which a heavy bond is cleaved are combined.

[0180]

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In the general formula (12), R ¹ and R ² each represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group or a carboxylic acid group, preferably a hydrogen atom. R ³ represents a hydrogen atom, a halogen atom such as a chlorine atom or a bromine atom, or an alkyl group such as a methyl group or an ethyl group, and is preferably a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group or a naphthyl group. Y represents a phenylene group or a naphthylene group including those having a substituent; examples of the substituent include an alkyl group such as a methyl group and an ethyl group; a halogen atom such as a chlorine atom and a bromine atom; a carboxylic acid group; a methoxy group and an ethoxy group. Examples thereof include an alkoxy group such as a group, a hydroxyl group, a sulfonic acid group, a cyano group, a nitro group, and an acyl group, and preferably have no substituent or are substituted with a methyl group. X is a divalent organic group linking a nitrogen atom and an aromatic carbon atom, and l represents an integer of 0 to 5, and preferably 1 is 0.

Further, a novolak resin, a polymer having a hydroxystyrene unit, and a polymer having a structural unit represented by the general formula (12) can be used in combination.

Further, a lipophilic resin can be added to the lithographic printing plate material of the present invention in order to improve the oil sensitivity of the composition. Examples of the lipophilic resin include a condensate of a phenol substituted with an alkyl group having 3 to 15 carbon atoms and an aldehyde, for example, t-butylphenol formaldehyde as described in JP-A-50-125806. Resin or the like can be used.

[2] Method of preparing lithographic printing plate material The lithographic printing plate material of the present invention is dissolved in the following solvent that dissolves each of the above components, and these are coated on a suitable support surface and dried. Obtained by providing a photosensitive layer.

Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone and the like. No. These solvents can be used alone or in combination of two or more.

The pH of the coating solution is preferably 3.5 or more and 8.0 or less, more preferably 4.0 or more and 6.5 or less in order to improve storage stability and suppress a decrease in reproducibility of small spots with time after exposure. . If the value is 3.5 or less, the above effect cannot be expected.

At the time of measurement, a photosensitive layer coating solution was prepared by dissolving a solid content of 10% by weight in an arbitrary organic solvent, water or a plurality of mixed solvents used for coating, and used as a measuring device by Toa Denpa Kogyo Co., Ltd. ) Digital pH meter HM-3
After the pH meter was standardized as a measurement condition using 0S, the measurement part of the pH meter was lowered vertically to the coating solution to be measured, and the measured value when immersed in the coating solution for 2 minutes was defined as the pH of the coating solution. .

For the same purpose, the film surface pH of the photosensitive layer is set at 4.
It is preferably 0 or more and 8.0 or less, more preferably 5.0 or more and 7.0 or less.

For measurement, 2 g of the photosensitive layer was placed on the support.
/ M ² was prepared, and a digital pH meter HM-18B of Toa Denpa Kogyo KK was used as a measuring device. After standardizing the pH meter as a measuring condition, 10 μl of pure water was measured with a micropipette. The pH value was dropped on the printing plate obtained for measurement, the measuring part of the pH meter was lowered vertically to the water droplet, and the pH value was set on the film surface of the photosensitive layer.

As the support, aluminum, zinc,
Metal plates such as steel, copper, etc., and metal plates, paper, plastic films and glass plates, plated or deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper coated with resin, metal foil such as aluminum Paper, hydrophilically treated plastic film, and the like. Of these, the aluminum plate is preferred. When the present invention is applied to a photosensitive lithographic printing plate, it is preferable to use, as a support, an aluminum plate which has been subjected to surface treatment such as graining treatment, anodic oxidation treatment and, if necessary, sealing treatment. A known method can be applied to these processes.

Examples of the graining method include a mechanical method and an electrolytic etching method.
Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buff polishing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material and the like.

For etching by electrolysis, phosphoric acid,
It is carried out using a bath in which inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid are used alone or in combination of two or more. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous solution of an alkali or an acid to neutralize and wash with water.

The anodic oxidation treatment is carried out by using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid or the like as an electrolytic solution, and using an aluminum plate as an anode for electrolysis. The amount of anodic oxide film formed is 1 to 50 m
g / dm ² is suitable, and preferably 10 to 40 mg / g.
dm ² , particularly preferably 25 to 40 mg / dm ² . The amount of the anodic oxide film is determined, for example, by immersing the aluminum plate in a chromic phosphate bath solution (prepared by dissolving 35 g of phosphoric acid 85% solution and 20 g of chromium (IV) oxide in 1 liter of water). It is determined by measuring the change in weight before and after dissolution of the coating on the plate.

Examples of the sealing treatment include a boiling water treatment, a steam treatment, a sodium silicate treatment, a dichromate aqueous solution treatment and the like. In addition, the aluminum plate support may be subjected to an undercoating treatment with a water-soluble polymer compound or an aqueous solution of a metal salt such as fluorozirconic acid.

As a method for applying the photosensitive layer to the surface of the support, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like are possible. is there. Although the amount of application varies depending on the application, for example, a photosensitive lithographic printing plate preferably has a solid content of 0.5 to 5.0 g / m ² .

The planographic printing plate material of the present invention has a wavelength of 700 n.
It is preferable to perform image exposure using a light source of m or more. As a light source, semiconductor laser, He-Ne laser, Y
An AG laser, a carbon dioxide laser and the like can be mentioned. The output is suitably 50 mW or more, preferably 100 mW or more.

As a developer used for development, an aqueous alkaline developer is preferable. The aqueous alkali developer includes, for example, aqueous solutions of alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tertiary sodium phosphate. . The concentration of the alkali metal salt is preferably used in the range of 0.05 to 20% by weight, more preferably 0.1 to 10% by weight.
It is.

The developer may contain an anionic surfactant, an amphoteric surfactant or an organic solvent such as alcohol, if necessary. As the organic solvent, propylene glycol, ethylene glycol monophenyl ether, benzyl alcohol, n-propyl alcohol and the like are useful.

[0199]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In addition, "part"
Indicates "parts by weight".

(Preparation of Support) A 0.24 mm-thick aluminum plate (material: 1050, tempered H16) was degreased in a 5% aqueous sodium hydroxide solution at 60 ° C. for 1 minute.
Temperature in a hydrochloric acid aqueous solution of 0.5 mol 1 liter;
The electrolytic etching was performed under the conditions of a current density of 60 A / dm ² and a processing time of 30 seconds. Then, after a desmut treatment at 60 ° C. for 10 seconds in a 5% aqueous sodium hydroxide solution, a temperature of 20 ° C., a current density of 3 A in a 20% sulfuric acid solution.
/ Dm ² , treatment time; 1 minute. Further, hot water sealing treatment was performed with hot water at 30 ° C. for 20 seconds to prepare an aluminum plate as a support for a lithographic printing plate.

Example 1 A coating solution for a photosensitive layer comprising a printing plate composition having the following composition was applied on the support so that the film thickness after drying was 2 g / m ^2, and dried at 100 ° C. for 2 minutes. Thus, a lithographic printing plate 1 was obtained.

(Composition of Coating Solution for Photosensitive Layer Positive Type) Binder A 60 parts Acid decomposition compound A 20 parts Acid generator A (TAZ-110) (manufactured by Midori Kagaku) 3 parts Infrared absorber Exemplified compound IR48 1 part Acid Proliferating agent Exemplified compound AI-1 5 parts Propylene glycol monomethyl ether 1000 parts
13 was obtained.

The film thickness of the negative photosensitive layer coating solution after drying is 2
g / m ² and dried at 100 ° C. for 2 minutes to obtain a lithographic printing plate 14.

(Composition of Photosensitive Layer Coating Solution Negative) Binder A 60 parts Acid insolubilizer A 40 parts Acid generator C 3 parts Infrared absorber Exemplified compound IR48 1 part Acid proliferator Exemplified compound AI-1 4 parts Propylene glycol Monomethyl ether 1000 parts The lithographic printing plate 15 was prepared by changing the coating solution of the photosensitive layer as shown in Table 1.
~ 18 was obtained. As comparative examples, planographic printing plates 19 to 22 were obtained.

* The compounds used are described below.

Binder A: a novolak resin obtained by copolymerizing phenol and m-, p-mixed cresol using formaldehyde (Mn = 3700, phenol: m-
Cresol: p-cresol molar ratio of 5: 5 respectively
7:38) Acid generator B: TFE-triazine (manufactured by Sanwa Chemical Co.) Acid generator C: 1-hydroxy-4-bromo-2-bromoacetylnaphthalene acid generator D: 4-methoxytrichloroacetanilide acid generator E: 2,4-bis (methanesulfonyloxy)
Butanolic acid generator F: ethanesulfonic acid ester (Synthesis example is shown below) 2.3 g of 2,3,4-trihydroxybenzophenone is dissolved in dioxane, and ethanesulfonyl chloride is dissolved in dioxane.
6 g are added dropwise. 2.3 g of potassium hydroxide is dissolved in water and added dropwise to the reaction solution. After continuing stirring for 3 hours, the reaction solution is poured into water. After adding salt in excess and salting out, the mixture was filtered and recrystallized from ethyl alcohol.

Acid Generator G: Methanesulfonic acid ester (Synthesis example is shown below) In a dry container, 0.49 g of anthropine and 0.81 g of methanesulfonyl chloride are dissolved in dioxane.
0.032 g of dimethylaminopyridine is added, and a dioxane solution of triethylamine is added dropwise to the reaction solution. After the dropping, stirring is continued for 3 hours, and then the reaction solution is dropped into water to precipitate a solid. After washing with filtered water, vacuum drying.

Acid insolubilizer A: (CKP-918 methylol group-containing resole resin: manufactured by Showa Polymer Co.) Acid insolubilizer B: hexamethoxymethylmelamine

[0209]

Embedded image

An image was formed on the obtained lithographic printing plate material by the following method.

(Positive type) semiconductor laser (wavelength 830n)
m, output: 500 mW). The laser beam diameter is 1 at 1 / e ² of the peak intensity.
It was 3 μm.

The resolution is 2 in both the scanning direction and the sub-scanning direction.
000 DPI. Developer SDR for positive type lithographic printing plate
-1 (manufactured by Konica Corporation) diluted with water to a volume ratio of 6 times 3
It was immersed in a developing solution at 0 ° C. for 30 seconds to elute and remove non-image areas (exposed areas), and then washed with water to produce a lithographic printing plate.

(Negative Type) Image exposure was performed on the surface of the photosensitive layer with a semiconductor laser similar to the positive type. The laser beam diameter was 13 μm at 1 / e ² of the intensity at the peak. The resolution was 2000 DPI in both the scanning direction and the sub-scanning direction. After the exposure, the photosensitive layer was heat-treated at 120 ° C. for 60 seconds using an infrared heater. Furthermore, the developer SDR for the positive PS plate
-1 (manufactured by Konica Corporation) diluted with water to a volume ratio of 6 times 3
Non-image area (unexposed area)
After the removal, the plate was washed with water to produce a lithographic printing plate.

The obtained planographic printing plate materials (positive type and negative type) were evaluated for the average line width of the image portion line generated by one laser scanning line by observation with an optical microscope.

(Evaluation of sensitivity) The sensitivity was determined from the exposure energy at which the average line width was 13 μm, and the evaluation was performed according to the following criteria.

[0216] ○ ··· 300mJ / cm ² or less ^{△ ··· 301~400mJ / cm 2 × ···} 401mJ / cm 2 or more.

(Evaluation of Raw Preservability) The obtained lithographic printing plate materials (positive type and negative type) were allowed to stand in a thermostat set at 55 ° C. for 5 days, and then the size was reduced to 50 cm × 100 cm. -Type PS plate developer SDR-1 (manufactured by Konica) was immersed in a 30 ° C. developer diluted with water to a volume ratio of 6 times at 30 ° C. for 30 seconds, and the image residual ratio of the plate photosensitive layer before and after immersion was determined by weight measurement. Was.

Plate photosensitive layer residual ratio% = (weight of photosensitive layer after development / weight of photosensitive layer before development) × 100 Positive negative type・ ・ ・: More than 90% ・ ・ ・: Less than 3% ・ ・ ・: 60 Not less than 90% not more than 3 to not more than 10% x not more than 60% x not less than 10%.

The results obtained are shown in Table 1 below.

[0220]

[Table 1]

As is evident from Table 1, the lithographic printing plate material of the present invention having an acid proliferating agent or a diazo compound has an excellent sensitivity and sufficient storage stability even when exposed to an infrared semiconductor laser. It can be seen that this is a planographic printing plate material corresponding to a negative type or a positive type that produces an effect.

[0222]

According to the present invention, a positive or negative type lithographic printing plate material having sufficient sensitivity and raw preservability even when exposed to an infrared semiconductor laser can be obtained by applying an acid multiplying agent to a photosensitive layer. It has a remarkably excellent effect.

On the other hand, when a diazo compound is applied to the photosensitive layer, a positive or negative lithographic printing plate material having sufficient sensitivity and raw preservability can be obtained even by exposure to an infrared semiconductor laser. It has the effect.

Claims (14)

[Claims] 1. A photosensitive layer containing a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond decomposable by an acid, an infrared absorbing agent and an acid multiplying agent on a support. A lithographic printing plate material characterized in that: 2. The method according to claim 1, wherein the acid proliferating agent is represented by the following general formula (1):
The lithographic printing plate material according to claim 1, which has the structure of (4). Embedded image (In the general formula (1), A ₁ represents a C _{1 to} C ₆ alkyl group or an aryl group, A ₂ represents a C _{1 to} C ₆ alkyl group, and A ₃ represents a bis (p-alkoxyphenyl) )
Represents a methyl group, a 2-alkyl-2-propyl group, a 2-aryl-2-propyl group, a cyclohexyl group or a tetrahydropyranyl group, and Z represents an acid represented by ZOH having an acid dissociation constant (pKa) of 3 or less. Indicates the residue. In the general formula (2), Z is as defined above, B ₁ is a hydrogen atom, an alkyl group or an aryl group, and B ₂ and B ₃ are methyl or ethyl groups or both form an ethylene or propylene group. , B ₄ represents a hydrogen atom or a methyl group. In the general formula (3), Z is as defined above, D _1, D ₂ represents a hydrogen atom, an alkyl group or an aryl group of up to _{C 1 ~C 6, D 2,} D 3 is C ₁ -C ₆ Or an alkylene or substituted alkylene residue forming an alicyclic structure with the alkyl group or both. In the general formula (4), Z has the same meaning as described above, and E represents a C _{1 to} C ₆ alkyl group or a phenyl group. ) 3. A photosensitive layer containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond decomposable by an acid, an infrared absorbing agent, and a diazo compound is provided on a support. A lithographic printing plate material characterized in that: 4. The diazo compound according to the following general formula (5)
4. The lithographic printing plate material according to claim 3, wherein the lithographic printing plate material has the structure of (6). Embedded image (In the general formula (5), R represents a hydrogen atom, an alkyl group or an aryl group, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkoxy group or an alkyl group, and X ⁻ represents a counter anion. Y represents -NH-, -O-, -S-, n represents an integer, In the general formula (6), A represents a condensable aromatic group, and R, R ₁ , R ₂ , R _3, X ^-,
Y and n have the same meanings as in the general formula (5). ) 5. The lithographic printing plate according to claim 1, wherein the compound having a bond decomposable by an acid has a structure represented by the following general formula (7). material. Embedded image (In the formula, R _{1 to} R ₄ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and any two of R _{1 to} R ₄ may combine to form a ring, and an ether bond And R _{1 to} R ₄ may be the same or different from each other. Further, each may have a substituent.) 6. The lithographic printing plate according to claim 1, wherein the compound having a bond decomposable by an acid has a structure represented by the following general formula (8). material. Embedded image (Wherein, R _5, R ₆ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, R _5, R _6
May combine to form a ring, or may have an ether bond, and R ₅ and R ₆ may be the same or different. Further, each substituent may be introduced. n and n 'represent an integer of 1 to 6, and m represents an integer of 1 to 80. ) 7. A photosensitive layer containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of being insolubilized in an alkali in the presence of an acid, an infrared absorbing agent and an acid multiplying agent on a support. A lithographic printing plate material characterized by being provided. 8. The method according to claim 1, wherein the acid proliferating agent is represented by the general formula (1):
The lithographic printing plate material according to claim 7, which has the structure of (4). 9. A photosensitive layer comprising, on a support, a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of being insolubilized in an alkali in the presence of an acid, an infrared absorber, and a diazo compound. A lithographic printing plate material characterized by comprising: 10. The lithographic printing plate material according to claim 9, wherein the diazo compound has the structure represented by the general formula (5) or (6). 11. The lithographic printing plate material according to claim 7, wherein the compound which is insoluble in alkali in the presence of an acid has a methylol group. 12. The compound according to claim 7, wherein the compound which can be insolubilized with respect to an alkali in the presence of an acid is at least one of a melamine resin and a resol resin.
A lithographic printing plate material according to any one of the above. 13. The lithographic printing plate material according to claim 1, wherein the infrared absorbing agent is a cyanine dye. 14. The photosensitive layer has a thickness of 700 to 2,000 nm.
2. The method according to claim 1, wherein the following wavelengths are responsive.
3. The lithographic printing plate material as described in 3.