JPH11153859A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable recording using semiconductor infrared laser beams and attainment of sufficient sensitivity even in the case of processing with an aqueous developing solution and shortening of developing time by forming a responsive layer containing a dye having an absorption peak in a specified region and a compound to be allowed to generate an acid by irradiation with heat or activating rays and a compound to be insolubilized in the developing solution in the presence of an acid and a resin soluble car dispersible in water, on a support. SOLUTION: This responsive layer contains the dye having the absorption peak in the wavelength region of 400-1200 nm, and the compound to be allowed to generate an acid by irradiation with heat or activcating rays and the compound to be insolubilized in the developing solution in the presence of an acid and the resin soluble or dispersible in water, on the support. This dye having the above absorption peak is an infrared absorber, and this water soluble or dispersible resin is the ones having phenolic hydroxyl groups or water-soluble latex particles. The compound capable of generating the acid by irradiation with heat or activated rays is an aminoplast. This responsive layer is imagewise exposed and then removed of the unexposed parts of the responsive layer by using the aqueous developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material which can be developed with water, and more particularly to an image forming material having a negative type sensitive layer capable of forming an image by exposure to infrared rays. Also, the present invention relates to a method for forming an image using the same.

[0002]

2. Description of the Related Art US Pat. No. 5,340,699 describes a printing plate material used for a plate making method which can be digitally recorded by an inexpensive and compact infrared semiconductor laser, that is, a CTP (computer to plate). Techniques are disclosed. That is, using an infrared-sensitive image-forming material having a photosensitive layer containing an acid generator, an acid crosslinking agent (resole resin), a binder (novolak resin) and an infrared absorber as constituent elements, performing image exposure and developing treatment This is a technique for obtaining a negative type image forming material by performing a heat treatment before. Thus, a dye capable of absorbing infrared laser light is required as an essential requirement, and the dye is contained in the photosensitive layer of the image forming material. This makes it possible to form an image by exposure to the infrared semiconductor laser or the like.

However, it is still necessary to use a conventional strong alkaline developer having a pH of 12 or more as a developer. However, there are points to be considered in the working environment, waste liquid treatment is complicated, and the cost is high. Not preferred.
In addition, it is a fact that sufficient sensitivity has not been obtained and that a development time is required.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to enable recording with an infrared semiconductor laser and develop using an aqueous developer having a pH of less than 12. Is to provide a suitable image forming material,
A second object is to provide an image forming method which has achieved sufficient sensitivity and reduced development time even when aqueous development is performed.

[0005]

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

1) a dye having an absorption peak at 400 to 1200 nm on a support, a compound capable of generating an acid upon irradiation with heat or active light, a compound capable of being insolubilized in a developer in the presence of an acid, and a water-soluble compound Or an image forming material having a sensitive layer containing a water-dispersible resin.

2) The image forming material as described in 1) above, wherein the dye having an absorption peak at 400 to 1200 nm is an infrared absorber.

3) The image forming material as described in 1) or 2) above, wherein the water-soluble or water-dispersible resin contains a phenolic hydroxyl group or is a water-dispersible latex particle.

(4) The image forming material as described in any one of (1) to (3) above, wherein the compound capable of generating an acid upon irradiation with heat or actinic rays is aminoplast.

5) An image characterized in that after the photosensitive layer of the image forming material according to any one of the above 1) to 4) is image-exposed, the photosensitive layer in an unexposed portion is removed using an aqueous developer. Forming method.

6) After exposure, before development, the sensitive layer is
(5) The image forming method as described in (5) above, wherein the heat treatment is performed at 0 ° C.

7) An image forming method comprising: exposing the sensitive layer of the image forming material described in 2) to an image with an infrared laser; and removing the unexposed portion of the sensitive layer using an aqueous developer. .

Hereinafter, the present invention will be described in detail.

The image forming material of the present invention comprises 40
A dye having an absorption peak at 0 to 1200 nm, a compound capable of generating an acid upon irradiation with heat or actinic light, a compound capable of being insolubilized in a developer in the presence of an acid, and a water-soluble or water-dispersible resin. It is characterized by having a layer.
First, a water-soluble or water-dispersible resin will be described.

[1] Image Forming Material (Water-Soluble or Water-Dispersible Resin) The water-soluble or water-dispersible resin (polymer compound) used in the present invention is a dry coating of 1 to 10 μm made of the resin. The membrane is 20-40 ° C. water,
Or a compound that can be removed using a developer of an aqueous solution containing 5% or less of alcohols and ethers. As specific examples thereof, vinyl polymers containing the following water-soluble monomers can be used.

1) Nonionic monomers acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide,
Diacetone acrylamide, diacetone methacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, bis (acrylamide) acetic acid, N
-Amide monomers such as isopropylacrylamide.

N-vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazolidone and N-vinylsuccinimide.

2-hydroxyethyl acrylate, 2-
Hydroxyalkyl acrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycerol dimethacrylate, and glycerol monomethacrylate.

Acrylates containing an alkylene glycol component such as polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, and monoalkyl ethers thereof.

N-methylolacrylamide, N-methylolmethacrylamide, methylenebisacrylamide, methylenebismethacrylamide, N, N '-(1,
2-dihydroxy) ethylenebisacrylamide, 1,
3,5-triacryloylhexahydro-s-triazine, vinyl alcohol, allyl alcohol, vinyl acetate and the like.

2) Anionic monomers acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid,
Carboxylic acid-containing monomers such as acrylamide-N-glycolic acid or alkali metal salts obtained by substituting them with Na, K or the like.

Vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 2-sulfopropyl acrylate, 2-sulfopropyl methacrylate, 2-acrylamido-2-methyl Sulfonic acid-containing polymers such as propane or alkali metal salts obtained by substituting them with Na, K or the like.

Phosphorus-containing polymers such as phosphorus-containing acrylate, phosphorus-containing methacrylate and phosphorus-containing acrylamide.

3) Cationic monomers Aminoalkyl acrylates such as 2-dimethylamino-ethyl acrylate and 2-dimethylamino-ethyl methacrylate and quaternary ammonium salts thereof.

Dimethylaminopropylacrylamide,
Aminoalkyl methacrylamides such as dimethylaminopropyl methacrylamide, acrylamido-3-methylbutyldimethylamine, methacrylamido-3-methylbutyldimethylamine, acrylamidomethyldimethylamine, methacrylamidomethyldimethylamine, and methacrylamidomethyldiethylamine; Grade ammonium salt.

2-vinylpyridine, 4-vinylpyridine, N-vinylimidazole, vinylbenzylammonium salt, diallylammonium salt and the like.

It is necessary to adjust the composition ratio of the above monomers according to the selected monomers and applications, but it is preferably 5 to 70%, particularly preferably 10 to 50%.

Other monomer components used in combination with the above monomers include acrylonitrile, methacrylonitrile,
Examples include styrene and its derivatives, alkyl acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, alkyl vinyl ether, and alkylene.

The weight average molecular weight (M
w) is preferably from 2000 to 100,000. As other water-soluble or water-dispersible resins, water-soluble or water-dispersible nylon, polyurethane, polyester, cellulose, gelatin and the like can be used.

As the water-soluble or water-dispersible resin, latex particles are preferably used. Such latex particles are preferably insoluble and dispersible in an organic solvent, and examples thereof include the following polymer compounds.

Polyacrylate or copolymer thereof, polyacrylonitrile or copolymer thereof, polystyrene or copolymer thereof, polyethylene or copolymer thereof, polyvinyl chloride or copolymer thereof, polyvinylidene chloride or copolymer thereof, polyvinyl acetate or copolymer thereof, resole resin Or a copolymer thereof, an ionomer resin, polymethyl methacrylate or a copolymer thereof, polybutadiene or a copolymer thereof, and the like.

These polymer compounds are copolymers with monomers having a polar group in the main chain or side chain. Preferred polar groups include -COOR,

[0033]

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(In the above formula, R represents a hydrogen atom, an alkyl group or a carbocyclic group.). Particularly preferred is a copolymer with a monomer having a quaternary nitrogen atom or a quaternary phosphorus atom. Among them, those having a quaternary nitrogen atom in the main chain are represented by the following general formula (1)

[0035]

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[0036] (X ^-. Is an anion, R represents an alkyl group or a carbocyclic radical, n is an integer) while others contain represented by the monomer units of the so-called ionene type, also 4 in the side chain
As a representative of those containing a secondary nitrogen atom, the following general formula (2)

[0037]

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[0038] ^- or one containing (X is an anion, R represents an alkyl group or a carbocyclic radical, n is an integer.) Represented by the monomer units methacryloxy alkylammonium,
The following general formula (3)

[0039]

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[0040] ^- binding (X is an anion, R represents an alkyl group or a carbocyclic represents a group.) Through the or those comprising monomer units of vinyl benzyl ammonium represented by the monomer units amide group of the vinyl benzyl ammonium The following general formula (4) described in JP-A-55-22766.

[0041]

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[0042] (X ^- is an anion, R represents an alkyl group or a carbocyclic group.) Those represented by.

On the other hand, an example of a monomer unit containing a quaternary phosphorus atom in the main chain is represented by the following general formula (5):

[0044]

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(X ⁻ represents an anion, R and R ′ represent an alkyl group or a carbocyclic group), and examples of the side chain include the following general formula (6):

[0046]

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(X ^- represents an anion, R represents an alkyl group or a carbocyclic group).

In each of the general formulas (1) to (6), specific examples of the anion represented by X ⁻ include, for example, a halogen ion, a sulfate ion, a phosphate ion, a sulfonate ion and an acetate ion. Can be Examples of the alkyl group represented by R and R ′ include groups such as methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, and decyl. Examples of the carbocyclic group include aryl, aralkyl, Each group includes cycloalkyl, for example, benzyl, phenyl, p-methylbenzyl, cyclohexyl, cyclopentyl and the like. In the above general formula, the alkyl group or carbocyclic group represented by R, which is bonded to N ⁺ or P ⁺ , may be the same or different.

These polymer compounds can be obtained by emulsion polymerization. It can also be obtained by converting the synthesized polymer into a latex.
In order to make it possible to use an oil-soluble ethylenically unsaturated compound and a photopolymerization initiator, these latexes are preferably dispersed in an organic solvent. Further, these latexes are intermolecularly crosslinked in the particles to enhance the stability to organic solvents.

That is, in a preferred embodiment, the particulate dispersion is a polyacrylate or a copolymer thereof.
A latex of polystyrene or a copolymer thereof, polyethylene or a copolymer thereof, polyvinyl chloride or a copolymer thereof, polyvinylidene chloride or a copolymer thereof, polyvinyl acetate or a copolymer thereof, and preferably, the latex has a polarity represented by the following general formula: It is a monomer having a group and a copolymer.

-COOR,

[0052]

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In the above formula, R represents a hydrogen atom, an alkyl group or a carbocyclic group.

More preferably, these latexes have a quaternary nitrogen atom or a quaternary phosphorus atom in the main chain or side chain, and are more preferably cross-linked intramolecularly in the particles, and particularly preferably an organic solvent as a dispersion medium. That is, is used.

The particle size of the particulate dispersion used in the present invention is preferably in the range of 10 nm to 1 μm. Particle size 1μ
If it is larger than m, the resolving power of the finally obtained image will be poor, and particles having a particle size smaller than 10 nm are substantially difficult to prepare.

In the present invention, the water-soluble or water-dispersible resin preferably contains a phenolic hydroxyl group in order to improve the sensitivity of the image forming material. As an example containing a phenolic hydroxyl group, a vinyl polymer composed of a vinyl monomer component containing a phenolic hydroxyl group can be used. As the monomer component, vinyl phenol, hydroxyphenyl methacrylamide,
Examples include hydroxyphenyl methacrylate, N-hydroxyphenylmaleimide monomer and derivatives thereof.

The above polymer compounds can be used alone or in combination of two or more. The type and composition ratio may be appropriately adjusted according to the sensitivity, developability, and other uses of the image forming material.

Next, another sensitive layer composition for forming the sensitive layer will be described.

(Compound capable of generating an acid upon irradiation with heat or actinic rays) Examples of the compound capable of generating an acid upon irradiation with heat or actinic rays (hereinafter referred to as an acid generator) include various known compounds and mixtures. . For example, diazonium, phosphonium, sulfonium, and iodonium BF ₄ ⁻ ,
Salts such as PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , and ClO ₄ ⁻ , alkylonium salts described in JP-A-4-42158, organic halogen compounds, orthoquinone-diazidosulfonyl chloride, and organic metal / organic halogen The compound is also a sensitive layer composition that forms or separates an acid upon irradiation with heat or actinic rays, and can be used as an acid generator in the present invention. In principle, all organic halogen compounds which are known as free-radical-forming photoinitiators are compounds which form hydrohalic acids and can be used as acid 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, an acid generator is preferred from the viewpoints of sensitivity of an organic halogen compound to 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 are described in JP-A-54-74728 and JP-A-55-74728.
-24113, JP-A-55-77742, JP-A-6
0-3626 and 2-halomethyl-1,3,4-oxadiazole-based compounds described in JP-A-60-138439 and JP-A-4-46344. 2-halomethyl-1,3,3
Preferred examples of the 4-oxadiazole-based acid generator are shown below.

[0062]

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S- having a halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (7) is preferable.

[0064]

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In the general formula (7), 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.

The following are examples of compounds of the s-triazine-based photoacid generator represented by the general formula (7).

[0067]

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[0068]

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[0069]

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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 acid generator preferably falls under any one of the following 1 to 3.

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 one alkali-soluble moiety include esters comprising a combination selected from the following.

Compounds having two or more hydroxyl groups and alkyl sulfonic acids, compounds having two or more phenolic hydroxyl groups and alkyl sulfonic acids, anthracene derivatives having two or more hydroxyl groups and sulfonic acids.

[0075] 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 acid 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. Thereby, the solubility in an alkaline aqueous solution can be controlled.

. Examples of the acid 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. An ester of a phenolic hydroxyl group and an alkyl sulfonic acid is exemplified. The alkyl group of the alkylsulfonic acid is the same as described above. The alkyl sulfonic acid ester used for the acid 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. Thereby, the solubility in an alkaline aqueous solution can be controlled.

[0077] Examples of the acid generator comprising an ester of an anthracene derivative having two or more hydroxyl groups and a sulfonic acid include esters of a hydroxyl group of a dihydroxyanthracene, trihydroxyanthracene, and tetrahydroxyanthracene with a sulfonic acid. As the sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid,
1,2-naphthoquinonediazidosulfonic acid is exemplified. The alkyl of the alkyl sulfonic acid is the same as described above. The sulfonic acid ester used for the acid generator has two hydroxyl groups.
It is not necessary that all of the hydroxyl groups of the compound containing more than one be an ester, and the hydroxyl groups may be left. Thereby, the solubility in an alkaline aqueous solution can be controlled.

The bromomethyl aryl ketone derivative 2 is preferably bromomethyl aryl ketone or dibromomethyl aryl ketone. 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'-bis (bromoacetyl) biphenyl,
1,3,5-tris (bromoacetyl) benzene, 1,
3,5-tris (dibromoacetyl) benzene, etc., and these can be used alone or in combination of two or more.

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

[0080]

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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 these compounds have high thermal stability and do not inhibit the solubility of the acid crosslinking agent in an aqueous alkaline solution, they can be suitable acid generators.

In the present invention, an organic halogen compound and a diphenyliodonium salt are preferred from the viewpoints of sensitivity in image formation by infrared exposure and storage stability. As the organic halogen compound, s-triazines having a halogen-substituted alkyl group are particularly preferred. The maximum absorption wavelength λmax of the acid generator is preferably from 200 to 350 nm, and the molar absorption coefficient ε at λmax is preferably 10,000 or more, particularly preferably 20,000 or more.

In the present invention, the acid generator may be used alone or in combination of two or more. The content thereof can be varied widely depending on its chemical properties and the composition of the sensitive layer or its physical properties. It is suitably in the range of about 0.1 to about 20% by weight, preferably 0.2 to 10% by weight, based on the dry weight of the product or the total weight of solids in the sensitive layer.

(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: And the like. The extent to which the solubility in alkali can be reduced may be such that the resin is completely insolubilized by finally insolubilizing it, such as by crosslinking with an alkali-soluble resin, so that the resin exhibits physical insolubility in total. Those which were originally alkali-soluble by the action of the acid insolubilizing agent due to actinic rays show insolubility in an alkaline solution used as a developer and remain 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 insolubilizer may further include 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, polymer having an aromatic compound having a methylol group, an alkoxymethyl group or an acetoxymethyl group in a molecule, aminoplast, a compound represented by the general formula (p), an alicyclic compound Alcohols and / or heterocyclic alcohols can be mentioned. Hereinafter, description will be made in order.

The silanol compound is one having an average of one or more hydroxyl groups bonded to silicon atoms 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.

Examples of the compound 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 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 polymer 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 preferably 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, if the molecular weight exceeds 50,000, the solubility in an aqueous alkali solution is not sufficient, and the pattern is deformed due to swelling, 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.

Compounds 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 formulas (a) to (d). Compounds.

[0097]

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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.

[0101]

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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.

As the alkali-soluble polymer having an aromatic ring having a methylol group, an alkoxymethyl group or an acetoxymethyl group in the molecule, one or two hydrogen atoms on the aromatic ring of the compound represented by the following general formula (h) are used. 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 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 formula (k) include, but are not limited to, the following.

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As the aminoplast, a melamine resin having a plurality of triazine nuclei bonded through a bond represented by the following general formula (l) or (m), and a melamine resin represented by the following general formula (n) or (o) The compounds represented can be used.

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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 sensitive 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.

As the heterocyclic alcohol, 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.

Among the acid insolubilisers used in the present invention, the most preferred are the above-mentioned aminoplasts.

(Dye having an absorption peak at 400 to 1200 nm) As a dye having an absorption peak at 400 to 1200 nm, for example, an infrared absorbing dye having an absorption at a wavelength of 700 nm or more, carbon black, magnetic powder and the like can be used. it can. Particularly preferred are the above-mentioned infrared absorbing dyes, which have an absorption peak at 700 to 850 nm and have a molar extinction coefficient ε of 10 ⁵ or more at the peak.

Examples of the infrared absorbing dyes 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.

As the infrared absorbing dye, a cyanine dye represented by the following general formula (8) or (9) is particularly preferred.

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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 a benzo-fused ring or a naphtho-fused ring which may have a substituent. 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 (8) or (9) include those which form a cation and have a counter anion. In this case, the counter anion is C
_{^{l -, Br -, ClO 4}} -, BF 4 -, include alkylboron arsenide of t- butyl triphenyl borate arsenide.

In the general formulas (8) and (9), the number of carbon atoms (n) in the chain of conjugated bonds represented by L is determined when a laser emitting infrared light is used as a light source for image exposure. It is preferable to select an effective value according to the transmission wavelength of the light. For example, Y at an emission wavelength of 1060 nm
When an AG 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. The halogen atom as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -SO ₃ M and -CO
A group selected from OM (M is a hydrogen atom or an alkali metal atom) is preferable. 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;-((CH ₂ ) _n —O
_{-) k - (CH 2)} m OR (n and m are each an integer of 1 to 3, k is 0 or 1, R represents an alkyl group having 1 to 5 carbon atoms);. R ₃ and R ₄ one of -R-SO ₃ M in the other -R-SO ₃ ^- (R is an alkyl group having 1 to 5 carbon atoms,
M represents an alkali metal atom); or R ₃ and the other while the -R-COOM of R ₄ is -R-COO ^- (R is an alkyl group having 1 to 5 carbon atoms, 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-C
OO ⁻ , and the other is preferably —R—SO ₃ M or —R-COOM.

The cyanine dye represented by the general formula (8) or (9) 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 dye 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 absorbing dye added is preferably in the range of 0.5 to 10% by weight. If the addition amount exceeds 10% by weight, the developability of the non-image area (exposed area) decreases, and if it is less than 0.5% by weight, the development resistance of the image area decreases.

The image forming 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.

(Dye 2) The dye is used for the purpose of obtaining a visible image by exposure (exposure visible image) and a visible image after development.

As the dye, those which change color tone by reacting with free radicals or acids can be preferably used.
The term “change in color tone” includes any of a change from colorless to a color tone and a change from color to colorless or a different color tone. Preferred dyes are those that form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (made by Hodogaya Chemical Co., Ltd.), Oil Blue # 603
(Manufactured by Orient Chemical Industries), Patent Pure Blue (manufactured by Sumitomo Mitsui Chemicals, Inc.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Paysic Fuchsin, Malachite Green, Oil Red, m-cresol Purple, rhodamine B, auramine, 4-p
Triphenylmethane-based, diphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes represented by -diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. Examples of the color changing agent that changes to the color tone of

On the other hand, examples of the color changing agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p '-Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p',
p "-tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, Primary or secondary arylamine dyes represented by p ', p "-triaminotriphenylmethane are exemplified. The proportion of the above-mentioned color changing agent in the sensitive layer composition is preferably 0.01 to 10% by weight, more preferably 0.0 to 10% by weight.
2 to 5% by weight. These compounds can be used alone or in combination of two or more. Particularly preferred pigments are Victoria Pure Blue BOH and Oil Blue # 6.
03.

(Binder) The sensitive layer may contain a resin that is insoluble in water and soluble in an aqueous alkaline solution. Examples of such a resin include a novolak resin, a polymer having a hydroxystyrene unit, and a polymer containing an acrylate monomer component.

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.

Examples of the polymer containing an acrylic acid ester monomer component include a copolymer containing a substituted or unsubstituted alkyl acrylate and a substituted or unsubstituted alkyl methacrylate monomer component. As such monomer components, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, benzyl acrylate, cyclohexyl acrylate, acrylic acid -2-chloroethyl, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, methacryldecyl, undecyl methacrylate, undecyl methacrylate, dodecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methacrylate- 2-chloroethyl, N,
N-dimethylaminoethyl methacrylate, glycidyl methacrylate and the like can be mentioned.

Preferred is a copolymer high molecular weight obtained by copolymerizing a mixture of the monomers described below.

1) Monomers having an aromatic hydroxyl group, for example, o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, o-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate and the like.

2) Monomers having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl acrylate Hydroxypentyl methacrylate,
6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

3) Monomers having an aminosulfonyl group, for example, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, m
-Aminosulfonylphenyl acrylate, p-aminophenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like.

4) Monomers having a sulfonamide group, for example, N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

5) α, β-unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.

6) Acrylamide or methacrylamides For example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-
Cyclohexylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) ) Methacrylamide and the like.

7) Monomers Containing Fluoroalkyl Groups For example, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate,
Octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

8) Vinyl ethers For example, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether.

9) Vinyl esters For example, vinyl acetate, vinyl chloroacetate,
Vinyl butyrate, vinyl benzoate and the like.

10) Styrenes For example, styrene, methylstyrene, chloromethylstyrene and the like.

11) Vinyl ketones For example, methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone and the like.

12) Olefins For example, ethylene, propylene, isobutylene, butadiene, isoprene and the like.

13) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

14) Monomers having a cyano group, for example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile,
-Cyanoethyl acrylate, o-cyanostyrene, m
-Cyanostyrene, p-cyanostyrene and the like.

15) Monomers having an amino group, for example, N, N-diethylaminoethyl methacrylate,
N, N-dimethylaminoethyl acrylate, N, N-
Dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide,
Acryloylmorpholine, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

The copolymer high molecular weight preferably has a weight average molecular weight of 10,000 to 200,000 as measured by GPC (gel permeation chromatography), but the weight average molecular weight is limited to this range. It is not something to be done.

The binder resins which can be used in combination with the above resins include polyester resins, polyvinyl acetal resins, polyurethane resins, polyamide resins, cellulose resins, olefin resins, vinyl chloride resins, styrene resins, polycarbonates, Examples include polyvinyl alcohol, polyvinyl pyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, and rubber-based resin. Further, a resin having an unsaturated bond in the resin, for example, diallyl phthalate resin and its derivative, chlorinated polypropylene and the like can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, so that it is suitably used depending on the application. be able to.

The content of these alkali-soluble resins in the sensitive layer is preferably in the range of 20 to 90% by weight, and more preferably in the range of 30 to 70% by weight.

It is preferable to use a novolak resin in combination with a polymer having hydroxystyrene units or a polymer containing an acrylate monomer component, and the mixing ratio is 30.
The range of / 70 to 95/5 is preferred.

Further, a lipophilic resin can be added to the sensitive layer in order to improve the oil sensitivity of the composition. Examples of the lipophilic resin include, for example, JP-A-50-1258.
No. 06, a condensate of a phenol substituted with an alkyl group having 3 to 15 carbon atoms and an aldehyde, for example, a t-butylphenol formaldehyde resin can be used.

It is also preferable to add a self-oxidizing compound such as nitrocellulose and metal powder, an ultraviolet absorber and the like to the sensitive layer.

[2] Method for Producing Image Forming Material The image forming material of the present invention is dissolved in the following solvent that dissolves the above-mentioned components, and these are coated on the surface of a suitable support and dried to form a photosensitive layer. Is obtained.

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 lactic acid. Examples include methyl, ethyl lactate, and dimethylacetamide. These solvents can be used alone or in combination of two or more.

The pH of the coating solution is adjusted to 3.5 or more to improve the storage stability and to suppress the decrease in the reproducibility of small spots over time after exposure.
0 or less, more preferably 4.0 or more and 6.5 or less. It is preferable to add a basic compound as such a pH adjuster. Basic compounds can capture protons, and specifically include inorganic or organic ammonium salts, organic amines, amides, urea and thiourea and derivatives thereof, thiazoles, pyrroles, pyrimidines, and piperazines. , Guanidines, indoles,
Imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines, Schiff bases, salts of weak acids with sodium or potassium, basic nitrogen-containing resins described in JP-A-8-123030 Organic basic compounds described in JP-A-9-54437, thiosulfonate compounds described in JP-A-8-212598, and heat-neutralized basic compounds described in JP-A-7-219217 (sulfonylhydrazide compounds, etc.)
Is mentioned. When a heat-neutralized basic compound is used, the sensitivity is greatly improved by heating after exposure and before development. Specific examples are described below.

As the amine compound, ammonium acetate,
Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-
Propylamine, di-n-propylamine, tri-n-
Propylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine, tetramethylenediamine , Hexamethylenediamine, tetramethylammonium hydroxide, aniline, methylaniline, dimethylaniline, diphenylaniline, triphenylaniline, o
-Toluidine, m-toluidine, p-toluidine, o-
Anisidine, m-anisidine, p-anisidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2,4-dinitroaniline,
2,4,6-trinitroaniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, p-aminobenzoic acid, sulfanilic acid, sulfanilamide, pyridine, 4-dimethylaminopyridine, piperidine, piperazine 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline,
1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-
Triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexylguanidine, 1,2,3
-Tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4 '
-Dithiomorpholine, morpholinium trichloroacetic acid,
Examples include 2-amino-benzothiazole, 2-benzoylhydrazino-benzotoazole, allyl urea, thiourea, methyl thiourea, allyl thiourea, ethylene thiourea and the like.

A specific compound of the Schiff base is represented by the following general formula (10)

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(Provided that R ₁ and R ₂ are hydrocarbon groups (eg, alkyl groups such as methyl group, isopropyl group, octyl group, heptadecyl group, cycloalkyl groups such as cyclobutyl group and cyclohexyl group, phenyl group, tolyl group, etc.) R ₃ is a hydrogen atom or a hydrocarbon group (R ₁ , R ₂
The same groups as mentioned above). ) In the molecule.

The compound having the above structure can be synthesized by condensation of an aldehyde or ketone with an amine.

Specifically, a condensation reaction between a polyvalent amine and a monovalent aldehyde or a monovalent ketone, a monovalent amine and a polyvalent aldehyde or a polyvalent ketone,
It can be synthesized by a polycondensation reaction between a divalent amine and a divalent aldehyde or a divalent ketone.

Examples of monovalent amines include methylamine, propylamine, n-butylamine, n-amylamine, n-heptylamine, n-octylamine, and n-octylamine.
Nanonylamine, n-decylamine, n-dodecylamine, n-tridecylamine, 1-tetradecylamine,
n-pentadecylamine, 1-hexadecylamine, n
-Heptadecylamine, 1-methylbutylamine, octadecylamine, isopropylamine, tert-butylamine, sec-butylamine, tert-amylamine, isoamylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, tert-octylamine, 1,2-dimethylbutylamine, 4-methylpentylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylpentylamine, cyclobutylamine, cyclopentylamine, cyclohexanemethylamine, cyclohexylamine, aniline, o-toluidine, m-Toluidine, p-toluidine, m-ethylaniline, p-ethylaniline, p-butylaniline and the like. Examples of divalent amines include methine diamine, ethylene diamine, 1,3-diaminopropane,
1,2-diaminopropane, 1,2-diamino-2-methylpropane, 2,5-dimethyl-2,5-hexanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 1,4-hexane Diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 4,
4'-methylenebiscyclohexaneamine, 1,2-diaminocyclohexane, 1,3-cyclohexanebismethylamine, benzidine, 4-aminophenyl ether, o-tolidine, 3,3'-dimethoxybenzidine,
o-phenylenediamine, 4-methoxy-o-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,3-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-
And diaminonaphthalene. Examples of monovalent aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 2-methylbutyraldehyde,
Ethyl butyraldehyde, valeraldehyde, isovaleraldehyde, hexanal, 2-ethylhexanal,
2,3-dimethylvaleraldehyde, octylaldehyde, cyclohexanecarboxaldehyde, cyclooctanecarboxaldehyde, phenylacetaldehyde, 2-phenylpropionaldehyde, diphenylacetaldehyde, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, o -Anisaldehyde, m-anisaldehyde, p-anisaldehyde, o-ethoxybenzaldehyde, p-ethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 4-biphenylcarboxaldehyde, 2-naphthaldehyde, etc. Examples of divalent aldehydes include o-phthalic dicarboxaldehyde, isophthalaldehyde,
Terephthaldicarboxaldehyde and the like. Further, examples of monovalent ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 3-methyl-
2-pentanone, 2-hexanone, 3-hexanone, 3
-Methylhexanone, 2-heptanone, 3-heptanone, 3-methylheptanone, 2-octanone, 3-octanone, 2-nonanone, cyclobutanone, cyclopentanone, phenylacetone, benzylacetone, 1-phenyl-2- Butanone, 1,1-diphenylacetone,
Examples include 1,3-diphenylacetone, 2-phenylcyclohexanone, 2-ylidene, β-tetralone, propiophenone, o-methylacetophenone, and benzophenone. Examples of divalent ketones include 2,4-pentane Dione, 2,3-hexanedione, 2,5-hexanedione, 2,7-octanedione, 2,3-butadione, 2-methyl-1,3-cyclopentadione, 1,3
-Cyclohexanedione, 1,4-cyclohexadione, 1,3-cyclopentanedione, 3-acetyl-2
-Heptanone, 2,2,6,6-tetramethyl-3,5
-Heptadione, 2-methyl-1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, dibenzoylmethane, 1,4-dibenzoylbutane, p-diacetylbenzene, m-diacetylbenzene, Benzyl, 4,4'dimethoxybenzyl, 2-phenyl-1,3-indandione, 1,3-indandione, o-dibenzoylbenzene, 1,2-naphthoquinone, 1,4-naphthoquinone and the like.

The following are specific examples of Schiff bases.

[0199]

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The basic compound can be used without any particular limitation in addition to the above compounds as long as it can capture protons.

These basic compounds may be used alone or in combination of two or more. The amount used is 0.0
It is preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5% by weight. When the content is 0.001% by weight or less, there is no effect of improving the storage stability and suppressing a decrease in reproducibility of small spots with time after exposure, and when the content is 10% by weight or more, the sensitivity is significantly reduced.

In the measurement, a photosensitive layer coating solution was prepared by dissolving a solid content of 10% by weight in any organic solvent, water or a plurality of mixed solvents used for coating, and used as a measuring device. ) 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. .

As a 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, an 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. These processes are described in JP-A-53-67507.
No. 53-77702, No. 53-123204,
Nos. 54-63902, 54-92804, 54
-133903, 55-128494, 56-
No. 28893, No. 56-51388, No. 58-424
No. 93, No. 58-209597, No. 58-19709
No. 0, No. 59-182967, No. 60-190392
No. 62-160291 and No. 61-182950
No. 63-99992, JP-A-1-150583
No. 1-154797, No. 1-176594, No. 1-188699, No. 1-188395, No. 1-2
Nos. 15591, 1-2242289, 1-2494
No. 94, No. 1-304893, No. 2-16090,
2-81692, 2-107490, 2-1
No. 85493, No. 3-104694, No. 3-1775
No. 28, No. 4-176690, No. 5-24376,
Nos. 5-24377, 5-139067, 6-2
A known method such as that described in Japanese Patent No. 47070 can be applied.

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 and 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 can be determined, for example, by immersing the aluminum plate in a chromic acid 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) to form an oxide film. It is determined by measuring the change in weight before and after dissolution of the coating on the aluminum plate.

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

On the back surface of the support, a coating layer made of a metal oxide obtained by hydrolysis and polycondensation of an organic metal compound or an inorganic metal compound, or an organic polymer, in order to suppress the elution of the anodic oxide film of aluminum. It is preferable to provide a coating layer made of a compound (hereinafter, referred to as a back coat layer).

The back coat layer may be used in such an amount as to suppress the elution of aluminum during development, and is preferably in the range of 0.001 to 10 g / m ² , more preferably 0.01 to 1 g / m 2. ² or less, 0.02
It is most preferably at least 0.1 g / m ² .

As a method for coating the back coat layer on the back surface of the aluminum support, various methods can be applied.
The most preferable method for securing the above-mentioned coating amount is a method of preparing a coating liquid for the back coat layer, coating and drying.

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

The image forming material of the present invention has a wavelength of 4
It is preferable to perform image exposure using a light source of 00 nm or more, particularly 700 nm or more. Examples of the light source include a semiconductor laser, a He-Ne laser, a YAG laser, a carbon dioxide laser, and the like. The output is suitably 50 mW or more per laser beam, preferably 100 mW or more.

[3] Image Forming Method As a method of forming an image on the image forming material of the present invention, the photosensitive layer is exposed imagewise, and then the exposed portion of the exposed layer is removed using an aqueous developer. It is preferable to use the above-mentioned infrared laser as a means for performing imagewise exposure. As a specific method, continuous processing is performed while adding a replenisher to the developer. In the present invention, since the sensitive layer component dissolved in the developer is limited to decomposed products that do not affect the developability, replenishment of the developer can be greatly reduced as compared with the conventional method, and therefore, the continuous use time of the developer can be reduced. , And a period in which replacement is unnecessary is secured for a long period of time, which leads to a large increase in the continuous processing amount. In addition, since the development process can be suppressed with a low replenishment, the amount of waste liquid can be reduced, and an excellent effect on environment and hygiene can be expected. Further, since a water-soluble or water-dispersible resin is used, an aqueous developing solution can be used, which is excellent in handleability and has a reduced influence on the environment, which is preferable.

In the present invention, the replenishment amount to the developer is preferably 100 ml or less per 1 m ² of the image forming material,
1 or less, especially 25 ml or less is most preferable. 1m ²
The replenishment amount per unit is an amount necessary for compensating for a decrease in the developer activity due to the development processing of the image forming material. To detect this, measure the processing area of the image forming material,
The method of measuring the conductivity, pH, and impedance of the developer, measuring the amount of the sensitive layer component mixed into the developer, and adding a preset replenishment amount to the developer is used. May be used. The timing of replenishment is optional as long as it does not affect the development stability in continuous processing. As a replenishment for factors other than the development processing of the image forming material, replenishment is performed to compensate for a decrease in developer activity due to carbon dioxide gas in the air, but the replenishment amount specified in the claims of the present invention is exclude. However, if the replenishment amount corresponding to the development processing of the image forming material can be reduced, it is obvious that the replenishment for the influence of the carbon dioxide gas can be greatly reduced, which contributes to the reduction of the waste liquid amount.

As the developing solution and the developing replenisher used for the development, an aqueous alkaline developing solution or an aqueous developing solution is preferable.

The aqueous developer may contain an organic solvent such as alcohols or ethers, or a surfactant in an amount of 0.1 to 10%.
It is preferable to use a developer having 5% by weight and having a pH of 4 to 12, preferably 6 to 11.

The aqueous alkali developing solution is, for example, an aqueous solution of an alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tertiary sodium phosphate. Is mentioned. 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.

The silicate concentration / alkali metal concentration (molar concentration of SiO ₂ / molar concentration of alkali metal) of the developing solution and the developing replenisher is preferably 0.15 or more and 1.0 or less, and the silicate concentration is the total weight. Is preferably 0.5 to 5.0% by weight. Particularly preferably, the silicate concentration / alkali metal concentration of the developer is from 0.25 to 0.75, the silicate concentration is from 1.0 to 4.0% by weight, and the silicate concentration of the developer replenisher / alkali metal. The concentration is 0.15 or more and 0.5, and the silicate concentration is 1.0 or more and 3.0% by weight or less.

Further, Japanese Patent Application Laid-Open Nos.
A non-silicic acid-based developer described in JP-160631 A can also be used.

An anionic, nonionic, cationic or amphoteric surfactant or an organic solvent can be added to the developer, if necessary.

Examples of the anionic surfactant include higher alcohol sulfates having 8 to 22 carbon atoms, such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate and secondary sodium alkyl sulfate. Salts, for example, aliphatic alcohol sulfates such as sodium salt of acetyl alcohol sulfate, for example, alkylaryl sulfonates such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, and sodium metanitrobenzene sulfonic acid; For example, C ₁₇ H ₃₃ CON (CH ₃ )
Examples include sulfonic acids of alkylamides such as CH ₂ CH ₂ SO ₃ Na, and sulfonates of dibasic fatty acid esters such as dioctyl sodium sulfosuccinate and sodium sulfosuccidihexyl ester.

As nonionic surfactants, JP-A-59 / 1984
Nos. -84241, 62-168160 and 62-
No. 175758, cationic surfactants disclosed in JP-A-62-175775, and amphoteric surfactants include, for example, alkyl carboxy betaine type, alkyl amino carboxylic acid type and alkyl imidazoline type compounds. Alternatively, an organic boron compound disclosed in Japanese Patent Publication No. 1-57895 can be used. The surfactant is suitably contained in the range of 0.1 to 5% by weight based on the total weight of the developing solution at the time of use.

Examples of the organic solvent include alcohols such as ethanol, n-propanol, i-propanol, butanol and benzyl alcohol, propylene glycol,
Glycols such as ethylene glycol, diethylene glycol, and triethylene glycol, and glycol ethers such as ethylene glycol monophenyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and diethylene glycol diethyl ether are useful.

The content of the organic solvent is preferably from 0.1 to 5% by weight based on the total weight of the developing solution at the time of use. 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.

The developer may further contain, if necessary, additives such as an alkali-soluble mercapto compound and / or thioether compound, a water-soluble reducing agent, an antifoaming agent and a water softener.

In the present invention, known gum solutions and rinsing solutions can be used. The gum solution is preferably added with an acid or a buffer for removing an alkali component of the developer, and may further contain a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like. When the gum solution contains a hydrophilic polymer compound, it also has a function as a protective agent for preventing scratches and stains on the plate after development.

The drying time is preferably from 1 to 5 seconds. When the drying time exceeds 5 seconds, the effect of the present invention cannot be obtained. If the drying time is less than 1 second, it is necessary to heat the plate surface to a very high temperature in order to sufficiently dry the photosensitive lithographic printing plate, which is not preferable in terms of safety and cost. As a drying method, a known drying method such as a warm air heater or a far infrared heater can be used. In the drying step, the solvent in the gum solution needs to be dried.

For this purpose, it is necessary to secure a sufficient drying temperature and heater capacity. The temperature required for drying depends on the components of the gum solution, but in the case of a gum solution in which the solvent is water, the drying temperature is usually preferably 55 ° C. or higher.
Heater capacity is often more important than drying temperature,
Its capacity is preferably 2.6 kW or more in the case of the hot air drying method. The larger the capacity, the better, but it is preferably 2.6 to 7 kW in terms of cost.

In the development processing of the present invention, for example, JP-A-5-15-1
A method using an automatic developing machine disclosed in Japanese Patent Application No. 88601 and Japanese Patent Application No. 9-143882 is effective. As the developing solution, erasing solution and post-processing solution, the processing agents described in Japanese Patent Application No. 8-56894 can be used.

After the exposure, the image forming material may be subjected to a heat treatment before the development. In this case, a heat treatment at 80 to 200C, preferably 80 to 150C for 5 to 100 seconds is preferable.

As a heating means, a known method such as radiation from an infrared heater or nip by a heating roll can be used.

Further, the image forming material after the development is
By performing the burning treatment at 0 ° C. for about 20 to 200 seconds, the mechanical strength of the sensitive layer can be dramatically improved, and when used as a printing plate, the printing durability can be greatly increased. When an infrared absorbing agent is used as the dye, it is preferable to perform image exposure with an infrared laser from the viewpoint of efficiency.

[0233]

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 photosensitive lithographic printing plate) Thickness 0.24
mm aluminum plate (material 1050, tempered H16) was degreased in a 5% aqueous solution of caustic soda for 1 minute.
Electrolytic etching was performed in a 0.5 mol aqueous solution of hydrochloric acid at a temperature of 25 ° C., a current density of 60 A / dm ² , and a processing time of 30 seconds. Then, 6% in 5% aqueous sodium hydroxide solution
After immersion at 0 ° C. for 10 seconds and desmutting, anodizing was performed in a 20% aqueous sulfuric acid solution at a temperature of 20 ° C. and a current density of 3 A / dm ² for 1 minute. It was further immersed in hot water of 30 ° C. for 20 seconds to perform sealing treatment, and dried at 80 ° C. for 5 minutes. On one side (back side) of this aluminum plate, JI
A No. S3 sodium silicate aqueous solution (10 g / l) was applied using a wire bar and dried at 90 ° C. for 2 minutes to prepare an aluminum support having a coating layer on the back surface. The coating layer was applied so as to have a dry weight of 10 mg / m ² .

Example 1 <Preparation of lithographic printing plate 1> A coating solution for a sensitive layer having the following composition was applied on the support so that the film thickness after drying was 2 g / m ² , and dried at 90 ° C. for 2 minutes. Thus, a lithographic printing plate material 1 was obtained.

(Coating solution for sensitive layer) Infrared absorbing dye (IR49) 1 part Acid generator (Exemplified compound (12)) 3 parts Hexamethoxymethyl melamine 20 parts Polymer compound methyl methacrylate / sodium acrylate 75 parts (composition ratio) 70/30 parts by weight of copolymer (Mw = 10000) Dye BOH 0.5 part Propylene glycol monomethyl ether 1000 parts An image was formed on the obtained lithographic printing plate material 1 by the following method. In addition, the said high molecular compound means the "water-soluble or water-dispersible resin" in this invention.

(Image Exposure and Development) The lithographic printing plate material 1 was subjected to image exposure using a semiconductor laser (wavelength: 830 nm, output: 500 mW). The laser beam diameter was 13 μm at 1 / e ² of the intensity at the peak. The resolution is the scanning direction,
The resolution was 2000 dpi in both the sub-scanning direction. During image exposure,
The lithographic printing plate material 1 was heat-treated at 120 ° C. for 1 minute, and then added to a developing solution (1% butyl cellosolve aqueous solution) at 27 ° C.
After immersion and development for 0 second to remove a non-image portion (unexposed portion), the plate was washed with water to produce a lithographic printing plate 1.

<Preparation of Lithographic Printing Plate 2> A lithographic printing plate 2 was prepared in the same manner as above except that the polymer compound was changed to a methyl methacrylate / 2-hydroxyethyl methacrylate copolymer.

<Preparation of Lithographic Printing Plate 3> A lithographic printing plate 3 was prepared in the same manner as described above except that the polymer compound was changed to a vinylphenol / 2-hydroxyethyl methacrylate copolymer.

<Preparation of Lithographic Printing Plate 4> A polymer compound was prepared by adding hydroxyphenyl methacrylamide / acrylonitrile / methacrylamide / 2-hydroxyethyl methacrylate / sodium acrylate (composition ratio: 20/10/40 /
A lithographic printing plate 4 was produced in the same manner as described above, except that the copolymer was changed to 20/10 Mw = 30,000).

<Preparation of Lithographic Printing Plate 5> A lithographic printing plate 5 was prepared in the same manner as above except that the polymer compound was changed to 50 parts of a methyl methacrylate / 2-hydroxyethyl methacrylate copolymer and 25 parts of the following compound A. Produced.

[0242]

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<Preparation of Lithographic Printing Plate 6> A polymer compound was prepared by mixing hydroxyphenyl methacrylamide / acrylonitrile / methacrylamide / 2-hydroxyethyl methacrylate / sodium acrylate (composition ratio 20/10/40 /
20/10 Mw = 30,000) copolymer, 50 parts of compound A
Lithographic printing plate 6 in the same manner as above except that the
Was prepared.

<Preparation of Lithographic Printing Plate 7> A lithographic printing plate 7 was prepared in the same manner as in the preparation of the lithographic printing plate 6 except that hexamethoxymethylmelamine was changed to tetramethoxybenzoguanamine.

<Preparation of Lithographic Printing Plate 8> A lithographic printing plate 8 was prepared in the same manner as in the preparation of the lithographic printing plate 6 except that hexamethoxymethylmelamine was changed to the following alkali-soluble acrylic copolymer.

(Synthesis of Alkali-Soluble Acrylic Copolymer) A mixed solvent of 125 ml of acetone and 125 ml of methanol was placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, a heater, and a nitrogen gas inlet tube. Then, 9.0 g of ethyl acrylate (0.
09 mol), 34.2 g of ethyl methacrylate (0.
30 mol), acrylonitrile 15.9 g (0.30
mol), 0.86 g of methacrylic acid (0.01 mol)
1), 35.2 g (0.2 m) of vinylbenzyl acetate
ol) and 51.6 g (0.30 mol) of 4-hydroxyphenyl methacrylamide. Further, 3.28 g of azobisisobutyronitrile was used as a polymerization initiator.
(0.02 mol), and the mixture was heated with vigorous stirring under a nitrogen stream and refluxed at about 60 ° C. for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then poured into water to precipitate a polymer compound. This was collected by filtration and dried under vacuum at 50 ° C. for 24 hours to obtain 100 g of an alkali-soluble acrylic copolymer. The yield based on the total amount of monomers was 90%.

The weight-average molecular weight of the obtained alkali-soluble acrylic copolymer was determined by (GPC) according to pullulan standard,
It was 50,000 as measured with N, N-dimethylformamide (DMF) solvent.

<Preparation of Lithographic Printing Plate 9> A lithographic printing plate 9 was prepared in the same manner as in the preparation of the lithographic printing plate 6 except that hexamethoxymethylmelamine was changed to 2,6-bis (1-hydroxyisopropyl) naphthalene. did.

<Preparation of Lithographic Printing Plate 10> A lithographic printing plate 10 was prepared in the same manner as in the preparation of the lithographic printing plate 6 except that the infrared absorbing dye was changed to IR25.

<Preparation of Lithographic Printing Plate 11> A lithographic printing plate 11 was prepared in the same manner as the preparation of the lithographic printing plate 6 except that the infrared absorbing dye was changed to IR29.

<Preparation of Lithographic Printing Plate 12> The lithographic printing plate 12 was prepared in the same manner as the lithographic printing plate 6 except that the infrared absorbing dye was changed to IR14 and a YAG laser was used for exposure.
2 was produced.

<Preparation of Lithographic Printing Plate 13 Comparative Example> A lithographic printing plate 13 was prepared in the same manner as in the preparation of the lithographic printing plate 1 except that the polymer compound was changed to the following novolak resin.

Novolak resin: phenol and m-, p-
Co-condensation compound of mixed cresol and formaldehyde (Mn = 500, Mw = 2500, phenol: m-cresol: p-cresol molar ratio is 20: 48: 3
2) <Preparation of Lithographic Printing Plate 14 Comparative Example> A lithographic printing plate 14 was prepared in the same manner as in the preparation of the lithographic printing plate 1 except that the polymer compound was changed to polyvinyl phenol described below.

The resulting planographic printing plates 1 to 14 were evaluated as follows.

(Sensitivity and Developing Time) Sensitivity was evaluated based on exposure energy (mJ / cm ² ) required for developing exposed portions. The time required for this is defined as the development time.

The results obtained are shown in Table 1 below.

[0257]

[Table 1]

As is clear from Table 1, the lithographic printing plates 1 to 12 adopting the present invention have good sensitivity and developability in a short time, and very good printed matter even when used as a printing plate. It can be seen that water-based development is possible. In particular, the lithographic printing plates 4 to 7 and 12 make the effects of the present invention remarkably excellent. However, since the planographic printing plates 13 and 14 for comparison do not contain any water-soluble or water-dispersible resin, they develop poorly and cannot be put to practical use.

[0259]

According to the present invention, excellent sensitivity is obtained even when aqueous development is performed, and a very good printed matter can be obtained even when used as a printing plate. It works.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/00 503 B41M 5/26 S

Claims (7)

[Claims] 1. A dye having an absorption peak at 400 to 1200 nm on a support, a compound capable of generating an acid upon irradiation with heat or actinic light, a compound capable of being insolubilized in a developer in the presence of an acid, and a water-soluble compound. Or an image forming material having a sensitive layer containing a water-dispersible resin. 2. The image forming material according to claim 1, wherein the dye having an absorption peak at 400 to 1200 nm is an infrared absorber. 3. The image forming material according to claim 1, wherein the water-soluble or water-dispersible resin contains a phenolic hydroxyl group or is a water-dispersible latex particle. 4. The image forming material according to claim 1, wherein the compound which can be insolubilized in an alkali in the presence of an acid is aminoplast. 5. The image forming method according to claim 1, wherein after the photosensitive layer of the image forming material according to claim 1 is image-exposed, the photosensitive layer in an unexposed portion is removed using an aqueous developer. Method. 6. The method according to claim 1, wherein after the exposure, before the development, the sensitive layer is coated with 80-150.
The image forming method according to claim 5, wherein the heat treatment is performed at a temperature of about 10 ° C. 7. The image forming method according to claim 2, wherein the sensitive layer of the image forming material according to claim 2 is subjected to image exposure using an infrared laser, and then the unexposed portion of the sensitive layer is removed using an aqueous developer. .