JPH1195416A - Lithographic printing plate material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve storage stability of a plate material even in an IR exposure system, to prevent blocking during storage, and to suppress decrease in reproducibility of small dots during storage after exposure by forming a photosensitive layer containing a compd. which can produce an acid by irradiation of active rays, an IR absorbent and a basic compd. on a supporting body. SOLUTION: This lithographic printing plate material consists of a supporting body and a photosensitive layer containing a compd. which can produce an acid by irradiation of active rays, a compd. having a bonded part which can be decomposed by an acid or can be changed into insoluble with an alkali in the presence of an acid, an IR absorbent and a basic compd. on the supporting body. The basic compd. used can trap protons. For example, inorg. or org. ammonium salts, org. amines, amides, urea and thiourea or derivs. of these, thiazoles, pyrroles, basic nitrogen-contg. resins, org. basic compds., etc., are used.

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. The present invention also relates to a method for producing the lithographic printing plate material.

[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.

In order to support CTP, the light source for exposure is changed from a conventional bright room printer using ultraviolet (UV) for a lithographic printing plate to a laser diode (L) using infrared (IR).
D) Digital recording is possible by changing to an exposure machine. However, compared with the UV exposure system, a problem peculiar to the IR exposure system is poor storage stability which is presumed to be caused by the inclusion of an infrared absorber in the photosensitive layer. Improvements are desired that go against the demands.

[0007] Apart from this, it is required that the small dot reproducibility of the printing plate does not fluctuate over time after exposure, or that the fluctuation be small, as good usability. In the case of the CTP type, small points can easily fluctuate with time due to a small amount of generated acid.
Further, there are problems such as deterioration of small point reproducibility due to blocking, and further improvement has been demanded.

[0008]

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, to achieve prevention of blocking during storage over time, It is an object of the present invention to provide a positive or negative planographic printing plate capable of suppressing a decrease in small-dot reproducibility during storage over time. Another object of the present invention is to provide a method for producing the lithographic printing plate.

[0009]

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

<1> On a support, there is provided 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 absorber and a basic compound. A lithographic printing plate material characterized in that:

<2> On a support, 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 particle size larger than the dry film thickness of the photosensitive layer. A lithographic printing plate material comprising a photosensitive layer containing a matting agent.

<3> A photosensitive layer having a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond decomposable by an acid, and an infrared absorber is provided on a support, and the surface of the photosensitive layer is provided on the surface of the photosensitive layer. A lithographic printing plate material comprising a matting agent.

<4> A coating solution for a photosensitive layer having a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond capable of being decomposed by an acid, and an infrared absorber is coated on a support together with a matting agent. A method for producing a lithographic printing plate material, characterized by being applied on top.

<5> On a support, a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond decomposable by an acid, and a photosensitive layer coating solution having an infrared absorber are provided. A method for producing a lithographic printing plate material, characterized by performing any one of the treatments.

A) Powdering a matting agent on the surface of the photosensitive layer b) Applying a matting agent dispersion on the surface of the photosensitive layer, drying and fusing to the surface of the photosensitive layer c) Dispersing a matting agent on the surface of the photosensitive layer A matting agent solution is sprayed, dried and fused to the surface of the photosensitive layer.

<6> Lithographic printing wherein <1> to <5> are replaced with "compounds which can be insolubilized in alkali in the presence of acids" as an alternative to "compounds having a bond decomposable by acid". Plate material and method of producing it (abbreviated as described above because of repetition).

In a preferred embodiment, the compound having a bond which can be decomposed by an acid has a structure represented by the above general formula (1) or (2), and is capable of being insolubilized in an alkali in the presence of an acid. That the compound has a methylol group, that the compound that can be insolubilized to alkali in the presence of an acid is at least one of a melamine compound and a resole resin, that the infrared absorber is a cyanine dye, that the photosensitive layer The pH of the surface is 4.0 or more and 8.0 or less, the pH of the photosensitive layer coating solution for forming the photosensitive layer is 3.5 or more and 8.0 or less, and the photosensitive layer is 700 or less.
Responding to a wavelength of at least 2,000 nm or less.

That is, the present inventors have proposed a system capable of forming an image by exposure to infrared rays, which has improved storage stability of a plate material,
Prevention of fluctuation of small spot reproducibility during storage over time after exposure, as a result of intensive studies to achieve prevention of blocking during storage over time, including a basic compound in the photosensitive layer, or It has been found that the incorporation of a matting agent having a particle size greater than or equal to the dry film thickness of the photosensitive layer, or that the above object can be achieved by allowing the matting agent to be present on the surface of the photosensitive layer, has led to the present invention. It has the ability to solve the above-mentioned problem by exposure in a system using infrared rays.

Hereinafter, the present invention will be described in detail.

The gist of the present invention is a lithographic printing plate material and a method for producing the same, which will be described below in order.

[1] Lithographic printing plate material The lithographic printing plate material of the present invention can be roughly classified into a basic compound-containing type and a matting agent-containing type according to its form, and both have a positive type and a negative type.

<1> Basic 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 basic compound.

In the present invention, the basic compound is a compound capable of capturing protons, and specifically includes inorganic or organic ammonium salts, organic amines, amides, urea and thiourea and derivatives thereof, thiazoles, pyrroles. , Pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines, Schiff bases, salts of weak acids with sodium or potassium A basic nitrogen-containing resin described in JP-A-8-123030, an organic basic compound described in JP-A-9-54437, a thiosulfonate compound described in JP-A-8-212598, and a heating method described in JP-A-7-219217. And basic compounds such as sulfonyl hydrazide compounds. 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 (3)

[0026]

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

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

Specifically, polyamines and monovalent aldehydes or monovalent ketones, condensation reaction of monovalent amines with polyvalent aldehydes or polyvalent ketones,
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.

[0032]

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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.

The photosensitive layer of this type of lithographic printing plate includes
It is also possible to add a mat agent described in detail below,
There are also two forms, that is, the form is contained in the photosensitive layer or the form is fixed to the surface of the photosensitive layer.

<2> Matting Agent-Containing Type The lithographic printing plate material of this type comprises: a) a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bonding portion decomposable by an acid, or an acid on a support. Containing a compound which can be insolubilized in alkali in the presence of an infrared absorber and a matting agent having a particle size not less than the dry film thickness of the photosensitive layer, or b) by irradiating the support with actinic rays A photosensitive layer having a compound capable of generating an acid, a compound having a bonding portion decomposable by an acid, and an infrared absorbing agent is provided, and a matting agent is provided on the surface of the photosensitive layer, specifically, fixed to the surface of the layer. Things.

Preferred examples of the matting agent (fine powder or fine particles) include polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid, polyacrylamide, alkyl polyacrylate, polystyrene and polystyrene derivatives. And copolymers using monomers forming these polymers, polyvinyl methyl ether, epoxy resin, phenolic resin, polyamide, polyvinyl butyral, silicon dioxide, diatomaceous earth, zinc oxide, titanium oxide, zirconium oxide, glass, alumina Dextrin, starch, calcium stearate, zinc stearate, polysaccharide fatty acid esters, synthetic polymers and the like.
These matting agents are preferably soluble in a developer,
It is desirable to select appropriately depending on the developer. For example, when a strongly alkaline aqueous solution is used as a developer, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, alkyl polyacrylate, polystyrene derivatives, and phenol resins are preferably used. Is done. When an organic solvent such as alcohols, glycols, and ketones is used as the other developer, a cellulose derivative, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyacrylic acid, polyacrylamide, or polyacrylamide may be used. Acrylic acid alkyl ester, polystyrene, acrylic acid alkyl ester, acrylamide, copolymer having styrene as one of the monomers, epoxy resin,
Phenol resins and the like are preferably used.

A matting agent composed of a fusible polymer for forming a melt adhered to the surface of the photosensitive layer is powdered (sprinkled, dispersed, or sprayed) on the surface of the photosensitive layer, and is subjected to heat treatment. The matting agent causes a melting phenomenon,
It solidifies as the temperature drops and forms a spherical hat-shaped melt.

Preferred as these matting agents are polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid,
Polyacrylamide, alkyl polyacrylate, polystyrene and polystyrene derivatives and copolymers using monomers of these polymers, polyvinyl methyl ether, epoxy resin, fusible phenol resin, polyamide, polyvinyl butyral, etc. Can be. It is desirable to appropriately select these depending on the phenomenon liquid of the photosensitive layer composition. For example, when a strong alkaline aqueous solution is used for the phenomenon liquid, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid , Polyacrylalkyl esters, polystyrene derivatives, and fusible phenol resins are preferably used. When organic solvents such as alcohols, glycols and ketones are used, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyvinylidene chloride, polyacrylate alkyl esters, polystyrene, epoxy resins, fusible phenols A resin and a copolymer containing at least one of acrylic acid, acrylamide, alkyl acrylate, and styrene as monomers are preferably applied.

The shape of the matting agent may be spherical, irregular, or another specific shape. The surface of the matting agent may be modified for the purpose of preventing aggregation of the matting agents. The average particle size of the matting agent is 0.1 when provided in the photosensitive layer.
1 to 30 μm is preferable, and 1 to 10 μm is more preferable. At this time, it is essential that a matting agent having a particle size larger than the dry film thickness of the photosensitive layer is present. On the other hand, when it is present on the surface of the photosensitive layer, the thickness is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm.

As a method of forming the matting agent, when the matting agent is incorporated in the photosensitive layer, the matting agent is added to the coating solution for the photosensitive layer and immediately after the matting agent is dispersed by ultrasonic dispersion. The photosensitive layer coating solution is applied to a support. On the other hand, when a matting agent is present on the surface of the photosensitive layer,
The amount of the photosensitive layer surface with the matting agent is 0.005 to 3 g / m ^2.
And more preferably 0.05 to 1 g / m ² .

As a specific method of causing the matting agent to be present on the surface of the photosensitive layer, for example, powdering the matting agent, directly applying a dispersion of the matting agent to the photosensitive layer, and fusing the matting agent to the surface when drying, A method of spraying (spraying) a dispersion or solution of the agent and fusing it to the surface at the time of drying can be used.

In order to apply a matting agent to the surface of the photosensitive layer by a powdering method, that is, to apply the matting agent in advance by a method such as a powder coating method, a fluid immersion method, an electrostatic powder spraying method, and an electrostatic fluidization immersion method. It is preferable to uniformly disperse or scatter on the photosensitive layer formed on the support. After the powdering, a matting agent can be fused to the surface of the photosensitive layer by appropriately performing a heat treatment (fusion treatment). The fusion process is performed using a heat source such as hot air or an infrared heater.
The matting agent is placed in a furnace heated to 30 ° C. or melted through a heating roll. At this time, some matting agents may be integrated with each other, and the obtained melt is fixed and dispersed in a spherical cap shape on the photosensitive layer, and the effect of preventing blocking of the present invention can be effectively exerted. . The contact between the matting agents is fixed to the surface and inside of the melt, but does not affect the printing plate.

A dispersion of the matting agent is applied directly to the photosensitive layer,
In the case of fusing to the surface during drying, an organic solvent or water that does not dissolve the photosensitive layer, a matting agent is added to a mixed solvent composed of a plurality of types, and the matting agent is immediately dispersed on the photosensitive layer by ultrasonic dispersion. This is achieved by applying a matting agent dispersion and drying.

When the dispersion of the matting agent is sprayed and fused to the surface during drying, this is achieved by spraying the ultrasonic dispersion of the matting agent on the surface of the photosensitive layer, drying and fusing the surface. You. As a dispersion solvent of the dispersion, water is preferable in terms of explosion proof, environmental suitability, workability and the like, and the content of the matting agent in the matting agent dispersion is desirably 10 to 30% by weight. As a spraying method, a known method such as an air spray method, an airless spray method, an electrostatic air spray method, an electrostatic atomizing electrostatic coating method, or the like can be adopted.

The photosensitive layer of this type of lithographic printing plate includes:
It is also possible to add the above-mentioned basic compounds, and the effects obtained thereby are also as described above.

Next, components 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 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 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.

[0051]

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S- having a halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (4) is preferable.

[0053]

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In the general formula (4), 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 (4)
-Examples of compounds of the triazine-based photoacid generator are shown below.

[0055]

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[0056]

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[0057]

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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 comprising a combination selected from the following compounds, 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.

Examples of the acid generator comprising an ester of a compound having two or more hydroxyl groups and an alkyl sulfonic acid include alcoholic hydroxyl groups such as ethylene glycol, propylene glycol, glycerin and 1,2,4-butanetriol; And esters with 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.

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 An ester of a phenolic hydroxyl group such as an acid ester 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 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.

Examples of the photoacid generator composed of an ester of a sulfonic acid and an anthracene derivative having two or more hydroxyl groups include, for example, esters of a hydroxyl group of a dihydroxyanthracene, a trihydroxyanthracene and a sulfonic acid of a tetrahydroxyanthracene. 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.

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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 thereof 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 with an acid) As the compound having at least one bond decomposable with an acid (hereinafter referred to as an acid-decomposable compound), specifically, 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.

Among 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 (1).

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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 formula (1), 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.

Specific examples of the compound represented by the general formula (1) include 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 (2).

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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 (1). 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.

The specific compound represented by the general formula (1) includes the following acid-decomposable compound B.

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

(Synthesis of Acid Decomposable Compound A) Cyclohexanone 0.5 mol, phenyl cellosolve 1.0 mol 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.

(Compounds 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 insolubilizers) 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 one having an average of one or more hydroxyl groups bonded to a silicon atom 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.

A compound having a carboxylic acid or a derivative thereof and a 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 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 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.

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.

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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.

Specific compounds include, 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.

As the phenylmethanol derivative,
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) can be 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 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).

[0117]

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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 the methylol form thereof 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 the following, but are not limited thereto.

[0121]

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[0122]

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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.

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.

(Infrared Absorbing Agent) As the infrared absorbing agent 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, anthraquino 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 (5) or (6) 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 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 (5) or (6) include those in which formula (5) or (6) forms a cation and has a counter anion. In this case, as the counter anion, Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ ,
Alkyl boron such as t-butyltriphenylboron and the like can be mentioned.

In the general formulas (5) and (6), the number of carbon atoms (n) of the conjugated bond chain represented by L is determined by using a laser which emits infrared rays 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 formula (5) or (6) 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 are not limited thereto.

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0151]

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[0153]

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[0154]

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[0155]

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[0156]

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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 (7), 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 hydroxystyrene copolymer described in JP-B-52-41050.

The polymer having the structural unit represented by the general formula (7) may be a homopolymer having a repeating structure composed of only the structural unit, or an unsaturated polymer of the structural unit and another vinyl monomer. Structural unit 1 represented by a structure in which a heavy bond has been cleaved
It is a copolymer combining at least one species.

[0165]

Embedded image

In the general formula (7), 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.

A novolak resin, a polymer having a hydroxystyrene unit, and a polymer having a structural unit represented by the general formula (7) 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 the above-mentioned 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.

In the 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 and the like as an electrolytic solution, and using an aluminum plate as an anode to perform 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 the 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 the developer used for the 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.

[0184]

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) An aluminum plate having a thickness of 0.24 mm (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 <Basic compound-containing type> A photosensitive layer coating solution 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 . After drying at 100 ° C. for 2 minutes, a lithographic printing plate 1 was obtained.

(Composition of Coating Solution for Photosensitive Layer Positive) Binder A 60 parts Acid-decomposable compound A 20 parts Acid generator A (TAZ-110) (manufactured by Midori Kagaku) 3 parts Infrared absorber Exemplified compound IR48 1 part Base Active compound N, N-dimethylaniline 1 part Propylene glycol monomethyl ether 1000 parts
12 was obtained.

The film thickness of the negative photosensitive layer coating solution after drying was 2
g / m ² and dried at 100 ° C. for 2 minutes to obtain a lithographic printing plate 13.

(Composition of photosensitive layer coating solution negative type) Binder A 60 parts Acid crosslinking agent A 40 parts Acid generator C 3 parts Infrared absorber Exemplified compound IR48 1 part Basic compound N, N-dimethylaniline 1 part Propylene Glycol monomethyl ether 1000 parts The lithographic printing plate 14 was prepared by changing the coating solution of the photosensitive layer as shown in Table 1.
~ 17. As comparative examples, planographic printing plates 18 to 23 were obtained.

An image was formed on the resulting 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.

[0196] ○ ··· 300mJ / cm ² or less ^{△ ··· 301~400mJ / cm 2 × ···} 401mJ / cm 2 or more.

(Evaluation of Raw Preservability) After the obtained lithographic printing plate material (positive type and negative type) was allowed to stand in a thermostat set at 55 ° C. for 5 days, the size was reduced to 50 cm × 100 cm to obtain a positive. -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.

Image residual ratio% = (weight after development / weight before development) × 100 Positive negative type・ ・ ・: More than 90% ・ ・ ・: Less than 3% ・ ・ ・: 60 to 90% △ ... 3 or more and 10% or less x ... less than 60% x ... More than 10%.

(Evaluation of reproducibility of small spots with time after exposure) (Positive type) semiconductor laser (wavelength: 830 nm, output: 50)
175 lines-2% halftone image exposure was performed on the surface of the photosensitive layer at 0 mW). The laser beam diameter is 1 / e ² of the intensity at the peak
Was 13 μm. The lithographic printing plate immediately after the exposure and one day after the exposure is applied to a positive PS plate developer SDR-1.
(Manufactured by Konica Corporation) was immersed in a developing solution at 30 ° C. diluted with water at a volume ratio of 6 times at 30 ° C. for 30 seconds, and the image area ratio of the printing plate photosensitive layer over time was determined by an optical microscope.

Image area ratio% = (Area after development one day after exposure / Area after development immediately after exposure) × 100 よ り: More than 90% 以上: 60 to 90% ×: 60 %Less than.

(Negative type) Image exposure was performed on the surface of the photosensitive layer with the same semiconductor laser as that of the positive type. The laser beam diameter was 13 μm at 1 / e ² of the intensity at the peak. After the exposure, the photosensitive layer was heated at 120 ° C. for 60 seconds using an infrared heater. The lithographic printing plate immediately after the exposure and one day after the exposure was placed in a 30 ° C. developer obtained by diluting a positive PS plate developer SDR-1 (manufactured by Konica) at a 6-fold volume ratio with water for 30 seconds. After immersion, the image area ratio of the printing plate photosensitive layer over time was determined by an optical microscope.

Image area ratio% = (area after development one day after exposure / area after development immediately after exposure) × 100 ○ ... less than 105% △ ・ ・ ・ 105 or more and 120% or less × ・ ・ ・ from 120 Many.

(Evaluation of Small Point Reproducibility) (Positive type) semiconductor laser (wavelength 830 nm, output 50)
175 lines-2% halftone image exposure was performed on the surface of the photosensitive layer at 0 mW). The laser beam diameter is 1 / e ² of the intensity at the peak
Was 13 μm. Immediately after the exposure, the positive PS plate developer SDR-1 (manufactured by Konica) was immersed in a 30 ° C. developer diluted to 6 times the volume ratio with water for 30 seconds, and the image area ratio of the printing plate photosensitive layer was measured optically. Determined by microscope.

Image area ratio% = (2% dot image area /
Actual image area after development immediately after exposure) × 100 ×: More than 90% Δ: 60 or more and 90% or less X: Less than 60%.

(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. After the exposure, the photosensitive layer was heated at 120 ° C. for 60 seconds using an infrared heater. Immediately after exposure, developer SDR for positive PS plate
-1 (manufactured by Konica) diluted with water to 6 times the volume ratio at 30 ° C
Of the printing plate photosensitive layer was determined by an optical microscope.

・ ・ ・: 95 or more and less than 105% Δ: 70 or more and less than 95%, and 105 or more and 120% or less ×: Less than 70% and 120% better.

* 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.

Crosslinking agent A: (CKP-918 methylol group-containing resole resin: manufactured by Showa Polymer Co., Ltd.) Basic compound: nitrogen-containing resin A (Synthetic example is shown below) 4-acetoxystyrene 11.4 g (0. 070 mol) and 4.8 g of dimethylaminomethylstyrene (0.0 g).
30 mol) in 1-methoxy-2-propanol 60 m
and heated to 65 ° C. V- as a polymerization initiator
25 (manufactured by Wako Pure Chemical Industries) 25 mg was added under a nitrogen stream and stirring. Further, 25 mg of V-65 was added every two hours for a total of three times. After the last addition, at 65 ° C for 2 hours, further 90 ° C
For 1 hour. The reaction mixture is methanol 600m
and 14.1 g of a white resin was obtained. 100 ml of methanol, 20 ml of water, and 25.5 g of a 25% aqueous solution of tetramethylammonium hydroxide were added to the resin, and the mixture was refluxed for 5 hours. After neutralizing the reaction mixture with acetic acid, it was poured into 800 ml of ion-exchanged water to obtain 10.5 g of a white resin. NMR measurement confirmed that the resin was nitrogen-containing resin A represented by Structural Formula A.
According to GPC measurement, the resin had a weight average molecular weight of 1
6,000.

Basic compound: Nitrogen-containing resin B (Synthetic example is shown below) 12.2 g of poly (p-hydroxystyrene) (manufactured by Maruzen Petroleum, weight average molecular weight 11,000), and 4-chloromethylpyridine 3 9.9 g (0.030 mol) was dissolved in N, N-dimethylacetamide (100 ml), potassium carbonate (4.2 g, 0.030 mol) was added, and the mixture was stirred at 120 ° C. for 5 hours. Thereafter, 1.2 g of acetic acid was added, and the mixture was added to 1 liter of ion-exchanged water. As a result, light brown resin 1
3.5 g were obtained. According to NMR measurement, this resin has the structural formula
It was confirmed that it was a nitrogen-containing resin B represented by the following formula: According to GPC measurement, the resin had a weight average molecular weight of 12,
000.

[0212]

Embedded image

The results obtained are shown in Table 1 below.

[0214]

[Table 1]

As is clear from Table 1, the lithographic printing plate material of the present invention having a basic compound has sufficient sensitivity and raw storability even when exposed to an infrared semiconductor laser, and suppresses a decrease in small point reproducibility. In addition, it can be seen that the lithographic printing plate material corresponds to a negative type or a positive type which has an excellent effect of suppressing a decrease in small point reproducibility during storage with time after exposure.

Example 2 <Mat Agent-Containing Type> A photosensitive layer coating solution comprising a printing plate composition having the following composition was dried on the support to a thickness of 2 g after drying.
/ M ² and dried at 100 ° C. for 2 minutes to obtain a lithographic printing plate a.

(Composition of Photosensitive Layer Coating Solution Positive Type) Binder A 60 parts Acid decomposition compound A 20 parts Acid generator A 3 parts Infrared absorber Exemplified compound IR48 1 part Propylene glycol monomethyl ether 1000 parts Are changed as shown in Table 2, and the planographic printing plates b to
c was obtained.

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

(Negative composition of photosensitive layer coating solution) Binder A 50 parts Binder B 10 parts Acid crosslinking agent A 40 parts Acid generator A (TAZ-110) (manufactured by Midori Kagaku) 3 parts Infrared absorber Exemplified compound IR48 2 parts Propylene glycol monomethyl ether 1000 parts The coating solution for the photosensitive layer was changed as shown in Table 1, and lithographic printing plates e to j were prepared as comparative examples. The lithographic printing plates a to d
The method of applying the matting agent is described below.

Lithographic printing plate a A matting agent containing a m-cresol formaldehyde novolak resin having a particle size of 0.5 to 2 μm and having a particle size of 0.5 to 2 μm, which was pulverized by a jet mill on the surface of the photosensitive layer and classified by a classifier, was sprayed at 0.05 g / m Powdering was performed uniformly with the amount of ² .

Lithographic Printing Plate b A matting agent containing a phenol formaldehyde novolak resin having a particle size of 1.0 to 3 μm and having a particle size of 1.0 to 3 μm was crushed on the surface of the photosensitive layer by a jet mill and classified by a classifier using a spray gun at a concentration of 0.1 g / m ² . Powdering was carried out uniformly with the applied amount. Next, it was left still in an infrared furnace heated to 150 ° C. for 20 seconds to fuse the matting agent to the surface of the photosensitive layer.

Lithographic printing plate c Polyvinyl alcohol was added to the surface of the photosensitive layer at a solid content of 20%.
% Aqueous solution was uniformly applied by air spray at a coverage of 0.05 g / m ² and dried in a thermostat at 100 ° C. for 5 seconds, and the dried droplets were used as a matting agent.

Lithographic printing plate d A photosensitive layer coating solution having the following composition was placed in a stainless beaker,
After immersion in an ultrasonic cleaner for 10 minutes and ultrasonic dispersion, the coating amount of the photosensitive layer coating solution on the support after drying was 2 g / m 2.
² and dried at 100 ° C. for 2 minutes to obtain a printing plate.

(Composition of Photosensitive Layer Coating Solution Positive Type) Binder A 50 parts Binder B 10 parts Acid crosslinking agent A 40 parts Acid generator A 3 parts Infrared absorber Exemplified compound IR48 1 part Matting agent (crushed with a jet mill) Classified by a classifier 3 parts Polycarbonate resin having a particle size of 1 to 3 μm) Propylene glycol monomethyl ether 1000 parts Evaluation of sensitivity and small-point reproducibility was performed in the same manner as in Example 1. The blocking was evaluated under the following conditions.

(Evaluation of Blocking) A lithographic printing plate material (common to negative and positive types) and an interleaving paper (manufactured by Konica) using the positive PS plate KM-3 were cut into 1 cm ² squares. And a weight of 10 Kg is placed thereon and a load of 10 Kg / cm ² is applied. In this state, it was allowed to stand in a thermostat at 55 ° C. for 24 hours, and the presence or absence of blocking was visually determined.

A: No blocking X: Blocking

The results obtained are shown in Table 2 below.

[0228]

[Table 2]

As is clear from Table 2, the lithographic printing plate material of the present invention having a matting agent has sufficient sensitivity even when exposed to an infrared semiconductor laser, and is excellent in suppressing a decrease in small-point reproducibility and blocking. It can be seen that this is a lithographic printing plate material corresponding to a negative type or a positive type having the above-mentioned effect.

[0230]

According to the present invention, by applying a basic compound to the photosensitive layer, sufficient sensitivity and raw preservability can be obtained even with exposure to an infrared semiconductor laser, and not only the suppression of small spot reproducibility reduction but also exposure A remarkably excellent effect is obtained in that a positive or negative type lithographic printing plate material which is excellent in suppressing a decrease in reproducibility of small spots during storage over time can be obtained.

On the other hand, by adding a matting agent having a particle size larger than the dry film thickness of the photosensitive layer to the photosensitive layer, or by providing a matting agent on the surface of the photosensitive layer, sufficient sensitivity and small dot reproduction can be obtained. A remarkably excellent effect is obtained in that a positive or negative type lithographic printing plate material excellent in suppression of deterioration in properties and antiblocking can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/20 505 G03F 7/20 505

Claims (22)

[Claims] 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 a basic compound is provided on a support. A lithographic printing plate material characterized in that: 2. The lithographic printing plate material according to claim 1, wherein the compound having a bond decomposable by an acid has a structure represented by the following general formula (1). 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.) 3. The lithographic printing plate material according to claim 1, wherein the compound having a bond decomposable by an acid has a structure represented by the following general formula (2). 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. ) 4. 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 absorber and a basic compound, on a support. A lithographic printing plate material characterized by being provided. 5. The lithographic printing plate material according to claim 4, wherein the compound which can be insolubilized to alkali in the presence of an acid has a methylol group. 6. The lithographic printing plate material according to claim 4, wherein the compound which can be insolubilized in an alkali in the presence of an acid is at least one of a melamine resin and a resol resin. 7. The lithographic printing plate material according to claim 1, wherein the infrared absorbing agent is a cyanine dye. 8. The pH of the surface of the photosensitive layer is 4.0 or more.
The lithographic printing plate material according to any one of claims 1 to 7, wherein the lithographic printing plate material is 0 or less. 9. The photosensitive layer coating solution for forming the photosensitive layer,
9. The lithographic printing plate material according to claim 1, wherein H is 3.5 or more and 8.0 or less. 10. The photosensitive layer has a thickness of 700 to 2000 nm.
10. Sensitive to the following wavelengths:
The lithographic printing plate material as described. 11. The lithographic printing plate material according to claim 1, further comprising a photosensitive layer containing a matting agent having a particle size larger than the dry thickness of the photosensitive layer. 12. The lithographic printing plate material according to claim 1, further comprising a matting agent on the surface of the photosensitive layer. 13. A support having a particle size greater than or equal to a dry film thickness of a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond capable of being decomposed by an acid, an infrared absorber, and a photosensitive layer. A lithographic printing plate material comprising a photosensitive layer containing a matting agent. 14. A photosensitive layer having a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond decomposable by an acid, and an infrared absorbing agent on a support, and a mat on the surface of the photosensitive layer. Lithographic printing plate material characterized by having an agent. 15. A coating solution containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound having a bond decomposable by an acid, and a photosensitive layer having an infrared absorbing agent together with a matting agent is coated on the support together with a matting agent. A method for producing a lithographic printing plate material, characterized by being applied to a lithographic printing plate material. 16. After a compound capable of generating an acid upon irradiation with actinic rays, a compound having a bond decomposable by an acid, and a photosensitive layer coating solution having an infrared absorber are provided on a support, any of the following: A method for producing a lithographic printing plate material, characterized by performing the above-mentioned treatment. a) Powdering a matting agent on the surface of the photosensitive layer b) Applying a matting agent dispersion to the surface of the photosensitive layer, drying and fusing the matting agent to the surface of the photosensitive layer c) A matting agent dispersion or matting agent solution on the surface of the photosensitive layer Is sprayed, dried and fused to the surface of the photosensitive layer. 17. The preparation of a lithographic printing plate material according to claim 16, wherein a matting agent is powdered on the surface of the photosensitive layer in step a), and then heat treatment is performed to fuse the matting agent to the surface of the photosensitive layer. Method. 18. 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 particles having a dry film thickness of a photosensitive layer or more on a support. A lithographic printing plate material comprising a photosensitive layer containing a matting agent having a diameter. 19. A photosensitive layer having 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, and an infrared absorbing agent on a support, A lithographic printing plate material comprising a matting agent on the surface. 20. A photosensitive layer coating solution containing a compound capable of generating an acid upon irradiation with an actinic ray, a compound capable of insolubilizing with respect to an alkali in the presence of an acid, and an infrared absorber together with a matting agent is coated on a support. A method for producing a lithographic printing plate material, characterized by applying. 21. After a photosensitive layer coating solution containing 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, and an infrared absorbing agent is provided on a support. And a method for preparing a lithographic printing plate material, comprising performing any of the following processes. a) Powdering a matting agent on the surface of the photosensitive layer b) Applying a matting agent dispersion to the surface of the photosensitive layer, drying and fusing the matting agent to the surface of the photosensitive layer c) A matting agent dispersion or matting agent solution on the surface of the photosensitive layer Is sprayed, dried and fused to the surface of the photosensitive layer. 22. The preparation of a lithographic printing plate material according to claim 21, wherein a matting agent is powdered on the surface of the photosensitive layer of a) and then heat-treated to be fused to the surface of the photosensitive layer. Method.