JPH086255A - Planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain such a planographic printing material for which any kind of supporting body can be used, good in ink buildup property eliminated from surface staining, and laying up plate is possible by forming a hydrophilic layer on a supporting body and forming a specified hardening layer and a photosensitive layer thereon. CONSTITUTION:At least one hydrophilic layer 2 is formed on a supporting body 1, on which a hardening layer 3 containing a polymerizable compd. and/or crosslinking polymer and at least one photosensitive layer 4 containing silver halide are formed. The binder included in the hydrophilic layer 2 is a hydrophilic polymer, and basically, gelatin is preferable. The hardening layer 3 is such a layer that can be hardened with radicals and contains at least one of polymerizable compds. and crosslinking polymers. The photosensitive layer 4 contains silver halide and has a function to produce radicals by image exposure and heat development. The radicals produced diffuse into the hardening layer 3 to harden the layer. Further, it is preferable that the photosensitive layer 4 contains a hydrophilic binder polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity direct lithographic printing material having the sensitivity of silver halide and capable of being written directly by visible or infrared laser light.

[0002]

2. Description of the Related Art A method of forming a polymer image by imagewise exposing a light-sensitive material containing a silver halide, a reducing agent and a polymerizable compound to develop the silver halide and thereby polymerizing the polymerizable compound in an image form. Are described in Japanese Patent Publication No. 45-11149. In this method, the polymerization is initiated by an oxidant radical of a reducing agent that has reduced silver halide (which may be a radical generated by decomposition of an oxidant of the reducing agent; hereinafter, simply referred to as an oxidant radical). There is.

On the other hand, a method of developing a silver halide by heating and forming a polymer image only by dry processing is described in JP-A-61-69062 and JP-A-61-73145. Further, a light-sensitive material suitable for producing a printing plate using this dry-process image forming method is described in JP-A-64-17047. Also, in JP-A-5-249667, JP-A-5-142782, JP-A-5-181285, JP-A-5-107764, and JP-A-5-281746, a polymerization layer and a halogen are provided on an aluminum support. A lithographic printing material provided with a light-sensitive layer containing silver halide is described. However, since the planographic materials described in these documents are based on the aluminum support, visible and infrared lasers (He-N
e, Ar, LD, etc., but imagesetters and scanners (eg SG757, SG608 manufactured by Dainippon Screen Co., Select set manufactured by Agfa, Accuset, Lino 30 manufactured by Lino) despite having sensitivity.
No. 0, Crossfield Magna 646, etc.) could not be mounted like a film support.

On the other hand, as a high-sensitivity printing plate which can be attached to a film support, the above-mentioned image setter using polyethylene laminated paper as a support, and a scanner, a silver digi plate manufactured by Mitsubishi Paper Mills Co.
There are set prints manufactured by fa. However, in these silver salt printing plates, it is difficult to control the inking of ink and background stains because of the lipophilic treatment of the physically developed silver transferred, and it is difficult to print. Many problems such as difficulty in using the plate, unstable running property, and recovery of processing liquid, probably due to the elution of a larger amount of silver than the plate material in the developing liquid was there.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a high-sensitivity direct lithographic material capable of utilizing not only an aluminum support but also any support such as a plastic support and a polyethylene laminated paper support. Is. Furthermore, it is an object to supply a direct lithographic material having good printability and good ink inking, no background stain, and plate setting. or,
It is an object of the present invention to provide a direct lithographic material processing system in which development processing is easy.

[0006]

At least one hydrophilic layer is provided on a support, and a polymerized layer containing a polymerizable compound and / or a crosslinkable polymer and a photosensitive layer containing silver halide are provided on the support. It was achieved by a lithographic printing material characterized in that both layers were provided.

The binder contained in the hydrophilic layer of the present invention is a hydrophilic polymer (for example, gelatin, starch, dialdehyde starch, carboxymethyl cellulose, gum arabic, sodium alginate, hydroxyethyl cellulose, polystyrene sulfonic acid, vinyl imidazole and acrylamide. However, gelatin is basically preferable.

It is preferable that gelatin is hardened. As a hardening agent, for example, inorganic compounds such as chrome alum, aldehydes such as formalin, glyoxal, malealdehyde and glutaraldehyde, and urea and ethyleneurea. N-methylol compounds, mucochloric acid, aldehydes such as 2,3-dihydroxy-1,4-dioxane, 2,4-dichloro-6-hydroxy-S
A compound having an active halogen such as a triazine salt or a 2,4-dihydroxy-6-chlorotriazine salt, divinyl sulfone, divinyl ketone or N, N, N-triacroylhexahydrotriazine, an active three-membered ring One or more of various compounds having two or more ethyleneimino groups or epoxy groups in a molecule and various compounds such as dialdehyde starch as a polymer hardener can be used.

Further, it is preferable that the hydrophilic layer contains fine powder (eg silica, TiO ₂ , zirconia, titania). The fine powder is preferably silica (SiO ₂ ), and the average particle size of the fine powder is preferably 0.1 to 10 μm. The hydrophilic layer may contain a pigment such as carbon black, a solid disperse dye, a dye dispersion, and a water-soluble dye for the purpose of preventing halation and improving plate inspection. The hydrophilic layer may be divided into two or more layers, in which case the proportion of fine powder to binder in each layer can be freely varied.

[Curable layer] The curable layer is a layer which can be cured by radicals (or other active species), and is considered to be cured by polymerization of a polymerizable compound and / or crosslinking of a crosslinkable polymer. . The curable layer needs to include at least one of a polymerizable compound and a crosslinkable polymer. Even when it contains a polymerizable compound, it is preferable to further contain a crosslinkable polymer. When the curable layer does not contain a crosslinkable polymer, it is preferable to contain a (non-crosslinkable) binder polymer in addition to the polymerizable compound. The binder polymer is preferably lipophilic. The curable layer may further contain a colorant if necessary. The coating amount of the curable layer is preferably 0.1 to 1
0 g / m ^2, more preferably from 0.3 to 5 g / m ^2. When the coating amount is 0.1 g / m ² or less, the cured image layer is too thin and the image strength (printing durability, etc.) is low. 10g /
When it is m ² or more, it is difficult to sufficiently cure the bottom surface of the curable layer. The coating amount of the polymerizable compound is 0 to 5 g / m ² , more preferably 0 to 3 g / m ² . The coating amount of the crosslinkable polymer or binder polymer is 0 to 7 g / m.
² , more preferably 0.1 to 5 g / m ² .

[Photosensitive layer] The photosensitive layer contains silver halide and has a function of generating radicals by imagewise exposure and thermal development. The generated radicals diffuse into the curable layer and cure it. The photosensitive layer preferably further contains a hydrophilic binder polymer. The light-sensitive material of the present invention is
Layers other than the photosensitive layer or other curable layers (the types and addition amounts of polymerizable compounds are the same for other layers)
Is characterized by containing a polymerizable compound. The polymerizable compound contained in layers other than the curable layer is the same as the polymerizable compound used in the curable layer. When the solvent of the coating liquid for the photosensitive layer is water, if the polymerizable compound is water-soluble, it may be dissolved in the coating liquid as it is. When the polymerizable compound is insoluble in water, it can be added by emulsifying or dispersing it in water or an aqueous solution of a hydrophilic binder polymer. The coating amount of the photosensitive layer was 0.
1 to 30 g / m ² , more preferably 0.5 to 10 g / m
It is in the range of ² . The content of the polymerizable compound in the photosensitive layer is in the range of 1 to 50% by weight, more preferably 3 to 30% by weight, based on the total amount of the photosensitive layer. Development by heat can be performed by providing the following image formation promoting layer on the photosensitive layer.

[Image formation promoting layer] The image forming promoting layer is a layer containing at least one of a reducing agent, a base, a base precursor and a thermal development accelerator. The image formation promoting layer,
It is particularly preferred to include a base precursor. The image formation promoting layer is preferably provided on the photosensitive layer as shown in FIGS. 5, 6, 7, 8, 9 and 11. The image formation promoting layer generally contains a hydrophilic polymer. However, a hydrophobic polymer can also be used, for example, a hydrophobic polymer can be dissolved in a solvent and applied, or a polymer latex can be applied. In this case, after thermal development, the image formation promoting layer including the emulsion layer is peeled off and removed prior to etching. When the image formation promoting layer is arranged on the surface of the light-sensitive material (the side farthest from the support), it is preferable to include a matting agent. The matting agent reduces the tackiness of the layer surface and prevents adhesion when the light-sensitive materials are stacked.
The coating amount of the image formation promoting layer is 0.3 to 30 g / m ² , and more preferably 1 to 10 g / m ² .

In addition, the present invention includes an embodiment in which the layers other than the above-mentioned photosensitive layer and image formation promoting layer contain a polymerizable compound. In the present specification, a layer containing a polymerizable compound other than the curable layer, the photosensitive layer and the image formation promoting layer is referred to as a “polymerizable compound-containing layer”. The polymerizable compound-containing layer may have a function of an overcoat layer, an intermediate layer or an undercoat layer described below. The polymerizable compound-containing layer generally contains a hydrophilic polymer. When the curable layer does not contain a crosslinkable polymer, two layers, a curable layer and a polymerizable compound-containing layer, are present as layers containing a polymerizable compound.

[Overcoat layer] The overcoat layer protects the light-sensitive material or prevents penetration of oxygen in the air,
It has the function of increasing the degree of curing of the polymerizable layer. The details of the overcoat layer are the same as those described above except that the overcoat layer does not contain a component that accelerates image formation (eg, base or base precursor, reducing agent, thermal development accelerator). The same).

[Intermediate Layer] An intermediate layer can be provided between each layer or between the support and the coating layer. The intermediate layer has a function as, for example, an antihalation layer containing a colorant, and a barrier layer that prevents components from diffusing between layers or mixing during storage of the photosensitive material. The material for the intermediate layer is arbitrary, but for example, the same hydrophilic polymer as that for the photosensitive layer or the overcoat layer can be used. The coating amount of the intermediate layer is about 10 g /
It is preferably m ² or less.

[Undercoat layer] As components constituting the undercoat layer, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid, amino alcohol (eg, monoethanolamine, diethanolamine, triethanol). Amine, tripropanolamine) and salts thereof (eg, hydrochloride, oxalate, phosphate), monoaminomonocarboxylic acid (eg, aminoacetic acid, alanine), oxyamino acid (eg, serine, threonine, dihydroxyethylglycine) ), Sulfur-containing amino acids (eg, cysteine, cystine), monoaminodicarboxylic acids (eg, aspartic acid, glutamic acid), diaminomonocarboxylic acids (eg, lysine), amino acids having an aromatic nucleus (eg, p-hydroxyphenylglycine) , Phenylalani , Anthranilic acid), amino acids having a heterocycle (eg, tryptophan, proline), aliphatic aminosulfonic acids (eg, sulfamic acid, cyclohexylsulfamic acid) and (poly) aminopolyacetic acid (eg, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). Note that the above-mentioned acids include those in which some or all of the acid groups form salts (eg, sodium salts, potassium salts, ammonium salts). Two or more of these components may be used in combination.

[Support] As the support, paper, synthetic paper,
Paper laminated with synthetic resin (eg polyethylene, polypropylene, polystyrene), plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg aluminum, aluminum alloy, zinc, iron, copper) A paper or plastic film laminated or vapor-deposited with the above metals is used. Particularly when used for a lithographic printing plate, among the above supports, an aluminum plate, a polyethylene terephthalate film, a polycarbonate film, paper and synthetic paper are preferred. A composite sheet (described in Japanese Patent Publication No. 48-18327) in which an aluminum sheet is bonded onto a polyethylene terephthalate film is also preferable. In addition,
The paper support is described in JP-A-61-3797 and JP-A-61-112150.

The case where an aluminum plate is used as the support will be described below as an example. The support is subjected to a surface treatment such as surface roughening treatment (graining treatment) or surface hydrophilic treatment, if necessary. Surface roughening treatment (graining treatment) is an electrochemical graining method in which an aluminum plate is grained by applying an electric current in a hydrochloric acid or nitric acid electrolyte solution, and a wire brush grain is used to scratch the aluminum surface with a metal wire. Method, a ball grain method of graining the aluminum surface with a polishing ball and an abrasive, and a brush grain method of graining the surface with a nylon brush and an abrasive). Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent used include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of this alkaline solution is preferably in the range of 1 to 50% by weight, and the temperature of the alkaline treatment is preferably in the range of 20 to 100 ° C.
It is preferable that the amount of aluminum dissolved is 5 to 20 g / m ² . It should be noted that the smut removal treatment after the electrochemical surface roughening treatment is performed at a temperature of 50 to 90 ° C. for 15 to 65
A method of contacting with sulfuric acid having a concentration of wt% (JP-A-53-1).
2739 gazette) or Japanese Patent Publication No. 48-28123
The method described in the publication is effective.

The aluminum support surface-roughened as described above can be subjected to anodizing treatment or chemical conversion treatment, if necessary. The anodic oxidation treatment can be performed by a known method. Specifically, sulfuric acid, phosphoric acid,
A direct current or an alternating current is applied to aluminum in a solution containing chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. alone or in combination to form an anodized film on the aluminum surface. The anodizing conditions vary depending on the electrolytic solution used, but generally the concentration of the electrolytic solution is 1 to 80% by weight, the temperature of the electrolytic solution is 5 to 70 ° C,
Current density is 0.5-60 amps / dm ² , voltage is 1-
It is preferable that the electrolysis time is 100 v and the electrolysis time is in the range of 10 to 100 seconds. The anodic oxidation method is particularly preferably a method of anodic oxidation in sulfuric acid at a high current density (described in British Patent No. 1412768) or a method of anodic oxidation using phosphoric acid as an electrolytic bath (described in US Pat. No. 2511661).

Anodized aluminum plates are further described in US Pat. Nos. 2,714,066 and 318,146.
As described in each specification of No. 1, it is treated with an alkali metal silicate (for example, by a method such as dipping in an aqueous solution of sodium silicate), or the adhesion between the aluminum support and the polymerizable layer and the printing characteristics are improved. For the purpose of
An undercoat layer can be provided on the surface of the aluminum support. When it is intended to produce a lithographic printing plate, it is used as a so-called PS plate. Of these, all aluminum substrates that have been surface-treated can be preferably used.

[Silver Halide] As the silver halide,
Any grains of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. The silver halide grains have regular crystal shapes such as cubes, octahedra and tetradecahedrons, irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. It may have one or a combination thereof. The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains having a projected area diameter of up to about 10 microns. Also, for polydisperse emulsions, US Pat.
4628, 3655394 and British Patent 141
The monodisperse emulsion described in each specification of No. 3748 may be used. Further, tabular grains having an aspect ratio of about 5 or more can be used. Tabular grains are described in "Photographic Science and Engineering" by Gutoff,
14: 248-257 (1970); and U.S. Pat. Nos. 4,434,226, 4414310, 44.
33048, 4439520 and British Patent 21.
No. 12157 can be easily prepared by the method described in each specification. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide.

Silver halide grains include, for example, copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold and precious metals of Group VIII (eg, rhodium, iridium,
(Iron, platinum, palladium) can be added in the form of each salt in the form of particles during or after the formation of particles according to a conventional method. The specific method is described in US Pat.
No. 5432, No. 1951933, No. 2448060
No. 2628167, 2950972, 34
88709, 3737313, 3772031
No. 4,269,927. Also, Research Disclosure (RD) magazine, 13th
Volume 4, No. It is also described in 13452 (June 1975).

When an image is formed by high-intensity short-time exposure, iridium ions are added in an amount of 10 per mol of silver halide.
^-8 to 10 ^-3 mol is preferably used, and more preferably 10 ^-7 to 10 ^-5 mol.

It is also possible to combine two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like.

The silver halide is preferably used in the form of an emulsion. Silver halide emulsions are described, for example, in Research Disclosure, No. 17643 (December 1978),
22-23, "I. Emulsion preparation
and types) ”, and No. 18716 (November 1979), p.648. Silver halide emulsions are usually prepared after physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are
Disclosure Magazine, No. 17643 and No. 17643. 1
8716. N for chemical sensitizers
o. 17643 (page 23) and No. 18716 (64
For the spectral sensitizer, see page 8, right column). 17643
(Pages 23 to 24) and No. No. 18716 (page 648, right column) about the supersensitizer. 18716 (64
Page 9, right column ~). Further, known additives other than the above are also described in the above two Research Disclosure magazines. For example, regarding the sensitivity enhancer, No. No. 18716 (page 648, right column), No. 17643 (24
~ Page 25) and No. 18716 (Page 649, right column). As the silver halide, it is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-63-68830. The silver halide emulsion may be a negative type silver halide or an inversion type silver halide capable of directly obtaining a positive image.

[Organic Metal Salt] An organic metal salt can be used in combination with the silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Examples of the organic compound used for forming the organic silver salt include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and JP-A-61-29044.
The acetylene silver described in each of JP-A No. 4 and 64-57256 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is 0 per mol of silver halide.
It is used in an amount of -10 mol, more preferably 0-1 mol. Further, instead of the organic silver salt, the above-mentioned organic compounds constituting the organic silver salt may be directly added to the photosensitive material and partially reacted with silver halide in the photosensitive layer to be converted into an organic silver salt.

[Reducing Agent] The reducing agent is contained in the photosensitive layer or a layer (curable layer, image formation promoting layer) provided near the photosensitive layer. The reducing agent is more preferably contained in the photosensitive layer or the curable layer. The reducing agent has a function of reducing and developing silver halide and / or a function of accelerating (or suppressing) polymerization of the polymerizable compound (or curing of the crosslinkable polymer). Examples of the reducing agent having the above function include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones and 5-amino. Uracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. Examples of the reducing agent include those disclosed in JP-A-61-183640, JP-A-61-188535, JP-A-61-282841, JP-A-62-170836, and JP-A-62-183840.
-86354, 62-86355, 62-20
6540, 62-264041, 62-109.
No. 437, 63-254442, and JP-A 1-267.
No. 536, and Japanese Patent Application No. 63-296774.
No. 63-296775, JP-A-1-27175.
Nos. 1-54101 and 1-91162 (including those described as developers or hydrazine derivatives). For the reducing agent, see “The Theory of the Photographic Pro” by T. James.
cess ”4th edition, pages 291-334 (1977), Research Disclosure, Vol. 170, 1702.
No. 9, pp. 9-15 (June 1978), and ibid.
Vol. 176, No. 17643, pages 22-31, (197
(December 8th). Also, JP-A-62-21
As in the light-sensitive material described in Japanese Patent No. 0446, instead of the reducing agent, a reducing agent precursor that releases the reducing agent when heated or in contact with a base may be used. Of these reducing agents, those which have a basicity to form a salt with an acid can also be used in the form of a salt with an appropriate acid.
These reducing agents may be used alone, or as described in each of the above publications, two or more reducing agents may be mixed and used. As the interaction of the reducing agent in this case, firstly, promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity, secondly, silver halide (and / or Inducing the polymerization of the polymerizable compound (or suppressing the polymerization) via the redox reaction with the other reducing agent in which the oxidized form of the first reducing agent generated by the reduction of (organic silver salt) Can be considered. However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously. The reducing agent is used in the range of 0.1 to 10 mol, preferably 0.5 to 5 mol, per mol of silver halide. Specific examples of the reducing agent are shown below.

[0028]

Embedded image

[0029]

Embedded image

[0030]

[Chemical 3]

By adjusting the type and amount of the reducing agent, the polymerizable compound can be polymerized in either the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. When, for example, a hydrazine compound is used as a reducing agent, radicals are generated from an oxidant produced when the silver halide is developed, so that polymerization occurs in a portion where a latent image of silver halide is formed.
On the other hand, as a reducing agent, radicals are not generated (or hardly generated) from its oxidant, but the reducing agent itself or the oxidant has a polymerization inhibiting action (for example, 1-phenyl-3-pyrazolidones, hydroquinones). When a reducing agent such as is used), a polymerization initiator (radical generator) is used in combination with the reducing agent, so that the latent image of silver halide is not formed (the oxidizing agent is more preferable than the reducing agent). Has a strong inhibitory effect on polymerization) or a portion where a latent image is formed (when the reducing agent has a stronger inhibitory effect than the oxidant)
Polymerization occurs at. However, in this case, it is necessary to add a polymerization initiator, which is decomposed by heating or light irradiation and uniformly generates radicals, to the photosensitive material as described below. Regarding such an image forming method and a reducing agent used, JP-A-61-75342 and JP-A-6-75342 disclose.
1-243449, 62-70836, 62-
No. 81635, No. 63-316038, JP-A 2-1
No. 41756, No. 2-141757, No. 2-2072.
No. 54 and No. 2-262662, and U.S. Pat. No. 4,649,098 and EP Patent No. 0202490.

[Polymerization Initiator] As the thermal polymerization initiator, for example, 6-18 of “Addition Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan), edited by The Society of Polymer Science and the Society for Polymer Experiments, Editorial Committee
And azo compounds (for example, azobis (isobutyronitrile) 1,1′-azobis (1-cyclohexanecarbonitrile)) and peroxides (see, for example, JP-A-61-243449). For example, benzoyl peroxide, potassium persulfate, etc.) are used. As a photopolymerization initiator, "Chemical Review" by Oster et al.
Magazine, Volume 68 (1968), pages 125-151, Kosa
"Light-Sensitive System" by John Wiley & Sons,
1965) pp. 158-193 and Japanese Patent Laid-Open No. 61-7.
5342 and JP-A-2-207254, carbonyl compounds (for example, benzophenones, acetophenones, quinones, or commercially available photopolymerization initiators, for example, "Irgacure 651" manufactured by Ciba-Geigy Co., "Irgacure 907", etc.), halogen-containing compounds, redox couples of photoreducible dyes and reducing agents, organic sulfur compounds, peroxides, optical semiconductors, metal compounds and the like are used.

The polymerization initiator is used per 1 g of the polymerizable compound,
It is preferably used in the range of 0.001 to 0.5 g,
More preferably, it is used in the range of 0.01 to 0.2 g.

[Polymerizable Compound] As the polymerizable compound,
Examples thereof include compounds having addition polymerizability or ring-opening polymerizability. Examples of the compound having an addition polymerizable property include a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable property include a compound having an epoxy group.
Of these, addition-polymerizable compounds having an ethylenically unsaturated group are particularly preferable. Examples of the compound having an ethylenically unsaturated group include (meth) acrylic acid and salts or esters thereof, (meth) acrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers. , Vinyl esters, N-
There are vinyl heterocycles, allyl ethers, allyl esters and their derivatives. Of these, esters of acrylic acid or methacrylic acid are preferred. Specific examples include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate,
Hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate,
Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A
, A diacrylate of a condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane, a triacrylate of a condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol, a hydroxypolyether The polyacrylate, polypropylene glycol diacrylate, and the above-mentioned polymerizable compound in which part or all of the acryloyl groups are substituted with methacryloyl groups can be mentioned. These polymerizable compounds can also be selected and used from commercial products. As a specific example, Aronix M-309, M-310 manufactured by Toagosei Kagaku Kogyo Co., Ltd.
M-315, M-400, M-210, M-610
0, M-8030 and M-8100, Kayarad TMPTA, DPHA, DPC manufactured by Nippon Kayaku Co., Ltd.
A-60, R-604, R-551, R-330, R-
684, R-712, R-310, R-167, HX-
220, HX-620, SARTOM manufactured by Shin Nakamura Chemical Co., Ltd.
ER-454 and -9035 can be mentioned. These polymerizable compounds may be used alone or in combination of two or more kinds.

The crosslinkable polymer is a polymer which can be crosslinked in the presence of radicals, for example, a double bond to which (A) radical (polymerization initiation radical or growth radical in the polymerization process of the polymerizable compound) can be added. A polymer having a group in the main chain or side chain of the molecule, or (B) a polymer in which a main chain or side chain atom (hydrogen atom, halogen atom such as chlorine) is easily extracted to generate a polymer radical. For example, 147 of “Polymer Reaction” (edited by The Polymer Society of Japan, Kyoritsu Shuppan, 1978).
~ 192. As a specific example, JP-A-6
Polymers having an ethylenically unsaturated double bond in the side chain of the polymer (eg, polymers of allyl (meth) acrylates (including copolymers), 1,2-polybutadiene, as described in JP-A-4-17047). 1,2-polyisoprene, etc.), and polymers having unsaturated double bonds in the polymer backbone (eg, poly-1,4-butadiene, poly-1,4-isoprene (including copolymers), natural and synthetic) Rubber). It is not clear how these polymers actually crosslink. For example, in the case of the above-mentioned polymer of allyl methacrylate, hydrogen atoms of the allyl group are abstracted by radicals to generate allyl radicals, which are recombined with each other and crosslinked. Alternatively, a radical-added radical to the double bond of the allyl group may be further reacted with the same polymer or polymerizable compound to be crosslinked, and the like. The crosslinkable polymer has a molecular weight of about 1,000 to 500,000. It is preferably within the range. After curing the curable layer,
When the etching treatment is performed with an alkaline aqueous solution, the crosslinkable polymer preferably has an acidic group such as a carboxylic acid group, a sulfonic acid group, a sulfonimide group, a sulfonamide group or a phenol group in the molecule. As an example,
Examples thereof include copolymers of (meth) acrylic acid, styrene sulfonic acid, maleic anhydride, etc. with the above-mentioned monomer having a crosslinkable group, and specific examples include allyl methacrylate-methacrylic acid copolymer, allyl methacrylate-
Examples thereof include styrene sulfonic acid copolymer. In the case of a copolymer, the molar content of the monomer having an acidic group is 1 to
70%, more preferably 5 to 50%.

[Curable Layer Binder Polymer] As the binder polymer used when the curable layer does not contain a crosslinkable polymer, a wide range of synthetic, semi-synthetic and natural polymer substances are generally used. Of these, oil-soluble polymers are preferable. The molecular weight of the binder polymer is preferably in the range of 1,000 to 500,000. Specific examples of the polymer include polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl acetate, vinyl acetate-ethylene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene. , Chlorinated polypropylene, polycarbonate, diacetyl cellulose, cellulose acetate butyrate, triacetyl cellulose, ethyl cellulose, polyvinyl pyridine, polyvinyl imidazole and polyurethane. These polymers can also contain acidic groups, if necessary, like the above-mentioned crosslinkable polymers. Further, these polymers can be used in combination with the crosslinkable polymer.

[Hydrophilic Binder Polymer] The hydrophilic polymer used as a binder polymer in the photosensitive layer, the overcoat layer or the image formation promoting layer is a polymer having a hydrophilic group or / and a bond in the molecule and is water-soluble. It may be either a polymer or a water-swellable polymer. As the hydrophilic group, a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group,
Examples include sulfonimide groups and amide groups. Examples of the hydrophilic bond include urethane bond, ether bond and amide bond. The water-swellable polymer is a polymer which has an affinity for water but is not completely dissolved in water because the polymer itself has a crosslinked structure and the like. The molecular weight of the hydrophilic polymer is preferably in the range of about 1,000 to 500,000. As the water-soluble or water-swellable polymer, a natural or synthetic polymer can be used. Examples of natural polymers include starch derivatives, cellulose derivatives, alginic acid, pectic acid, gum arabic, pullulan, dextran and other water-soluble polysaccharides, casein, and gelatin proteins. These may be artificially modified as necessary. Further, it may be modified or crosslinked during or after coating and drying. As the synthetic polymer, a polymer of a water-soluble monomer or a copolymer of this with another monomer can be used. Examples of the water-soluble monomer include monomers having a chemical structure such as a carboxyl group (and a salt thereof), an acid anhydride group, a hydroxyl group, a sulfonic acid (salt) group, an amide group, an amino group, and an ether group. Specific monomers are illustrated in "Applications and Markets of Water-Soluble Polymers" (CMC page 16-18). A copolymer obtained by crosslinking a polymer obtained by polymerizing (or copolymerizing) these monomers is also used (for example, the copolymer described in US Pat. No. 4,913,998).

As other synthetic polymers, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide and derivatives / modified products thereof can be used. In the case of polyvinyl alcohol, those having various degrees of saponification can be used, and copolymer-modified polyvinyl alcohol can also be used. Copolymerization modification is a method of saponifying a copolymer of vinyl acetate and another monomer to give modified polyvinyl alcohol. As the comonomer, any monomer can be used as long as it is a monomer that copolymerizes with vinyl acetate. Examples thereof include ethylene, higher vinyl carboxylate, higher alkyl vinyl ether, methyl methacrylate, and acrylamide. The post-modification is a compound reactive with a hydroxyl group of polyvinyl alcohol and modified by a polymer reaction. Examples thereof include those obtained by modifying the hydroxyl group with etherification, esterification, acetalization, and the like. Furthermore, crosslinked polyvinyl alcohol is also used. Examples of the crosslinking agent include aldehydes, methylol compounds, epoxy compounds, diisocyanates, divinyl compounds, dicarboxylic acids, and inorganic crosslinking agents such as boric acid, titanium and copper. These modified or cross-linked polyvinyl alcohols are described in "Poval", Vol. 3, "Polymer Publishing" (pp. 281-285).

In order to prevent oxygen from penetrating into the light-sensitive material and inhibiting polymerization or crosslinking, the hydrophilic binder polymer is preferably a substance having a low oxygen permeability. For example, the oxygen permeability coefficient is 1.0 × 10 ^-11 cc · cm /
It is preferably cm ² · sec · cm · Hg or less. As such a polymer, a polyvinyl alcohol-based polymer, gelatin, a vinylidene chloride copolymer and the like are preferable. Here, the polyvinyl alcohol-based polymer means polyvinyl alcohol and modified polyvinyl alcohol (for example,
Saponified block copolymers of polyvinyl acetate and other monomers). Molecular weight is about 1000-5
The range of 0,000 is preferable. Among these polymers, it is particularly preferable to contain a polyvinyl alcohol polymer having a saponification degree of 70% or more, more preferably 85% or more.

[Base and / or Base Precursor] The light-sensitive material of the present invention preferably contains a base or a base precursor. The base or the base precursor may be contained in any of the layers provided in the vicinity of the photosensitive layer, such as the curable layer, the photosensitive layer, the image formation promoting layer, etc. More preferably, it is contained. As bases and base precursors, inorganic bases and organic bases, or precursors of these bases (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.)
Can be used. As an inorganic base, JP-A-62-209
Inorganic bases described in Japanese Patent No. 448 and the like can be mentioned. Examples of organic bases include tertiary amine compounds described in JP-A-62-170954, bis-, tris- or tetra-amidine compounds described in JP-A-63-316760, and JP-A-64-68746. Screws described in Japanese Patent Publication No.
Examples thereof include tris- or tetra-guanidine compounds. A base having a pKa of 7 or more is preferable. From the viewpoint of storage stability of the light-sensitive material, it is preferable to use a base precursor rather than a base. As a base precursor, Japanese Patent Laid-Open No.
3-316760, 64-68746, 59-
Nos. 180537 and 61-313431, salts of organic acids and bases that are decarboxylated by heating, and urea compounds that release a base upon heating, such as those described in JP-A-63-96159. . Further, as a method of generating a base by utilizing a reaction, there is disclosed in JP-A-63-252
08, a reaction with a transition metal acetylide, a salt containing an anion having an affinity for a transition metal ion that is equal to or higher than the acetylide anion, and a poorly water-soluble base described in JP-A-1-3282. And a method in which a compound capable of complex-forming a metal compound and a metal ion constituting the compound with water as a medium are contained, and a base is released by a reaction between these two compounds in the presence of water. . The base precursor is preferably one that releases a base at 50 ° C to 200 ° C. For a light-sensitive material using a base or a base precursor, see JP-A-62-26.
It is described in Japanese Patent No. 4040. Further, a photosensitive material using a tertiary amine as a base is disclosed in JP-A-62-11.
No. 70954 discloses a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C., and a solubility of 0.1 is disclosed in JP-A No. 62-209523.
% Of guanidine derivative is disclosed in JP-A-63-70845, and a light-sensitive material using alkali metal or alkaline earth metal hydroxide or salt is disclosed in JP-A-62-209448. It is described in each. Further, a photosensitive material using an acetylide compound as a base precursor is disclosed in JP-A-63-
No. 24242 discloses a light-sensitive material which uses a propiolic acid salt as a base precursor and further contains silver, copper, a silver compound or a copper compound as a catalyst for a base generation reaction. Japanese Patent Application Laid-Open No. 63-81338 discloses a light-sensitive material containing the above-mentioned catalyst and the above-mentioned catalyst in a state of being separated from each other. JP-A-63-46447 discloses a light-sensitive material which uses a propiolic acid salt as a base precursor and further contains a heat-meltable compound as a reaction accelerator for a base-forming reaction in JP-A-63-97942.
JP-A-63-484 discloses a light-sensitive material containing a sulfonylacetate salt as a base precursor and a heat-meltable compound as a reaction accelerator for a base-forming reaction.
JP-A-63-96652 discloses a light-sensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base as a base precursor.
JP-A-63-173039 discloses a light-sensitive material containing a nucleophile as a decomposition accelerator of this compound.
There is a description in each publication. For a light-sensitive material using a bis or trisamidine salt of a decarboxylable carboxylic acid as a base precursor, see JP-A-64-9441.
The light-sensitive materials using bis or trisguanidine salts are described in JP-A-64-68749. The base and the base precursor can be used in combination. The amount of the base or base precursor used is in the range of 0.5 to 50 mol, preferably 1 to 20 mol, per mol of silver halide.

[Heat Development Accelerator] As the heat development accelerator,
Conventionally, it melts in the layer by heating and dissolves various substances
Compounds known as "hot solvents", eg US Pat.
347675, 3667959, Research
・ Disclosure magazine, December 1976, 26-2
Page 8, JP-A-62-151841, JP-A-62-1517.
43, 62-183450, 63-24383.
No. 5 and No. 63-253934
Len glycols, sulfonamides, cyclic amides, etc.
A heat fusible compound is used. As a thermal development accelerator
The binder polymer of the layer, at room temperature or heating
Compounds that sometimes have a plasticizing action, eg polymeric compounds
Known compounds known as plasticizers for
It Plasticizer is "Plastic compounding agent" Taiseisha, 21-
Page 26, "Plastic Additives (Second Edition)" (Hanser P
ublishers), Chapter 5, pp. 251-296, "Thermoplast
ic Additives "(Marcel Dekker Inc), No. 9, 345
Pp. 379, "Plastics Additives: An Industrial G
uide "(Noyes Plications), Chapter 14, 333-45
Page 8, "The Technology of Solvents and Plasticize
rs "(John Wiley & Sons Inc), Chapter 15, 903-1027.
page, ^"Industal Plasticizers "(Pergamon Press),
"Plastizer Technology Vol. 1" (Reinhold Publish
ing Corp), `` Plasticization and Plasticizer '' Proces
s ”(Ameran Chemistry). Compound
Depending on the object, distinguish between the above two functions
May be difficult, or may have both functions
It As a specific example of a particularly preferable heat development accelerator, urea,
Ethylene urea, methyl urea, dimethyl urea, ethyl urine
Element, urea such as propylene urea, acetamide, propylene
Amides such as onamides, sulfamides, sulfonamides
Mids, sorbitol, trimethylolethane, trime
Tyrol propane, pentaerythritol, glycerin
Ethylene glycol, propylene glycol, poly
Ethylene glycol, polypropylene glycol, pig
And polyhydric alcohols such as hexanediol and hexanediol
Examples include sugars, urea resins and phenol resins. What
Use two or more heat development accelerators in combination.
You can also

[Colorant] The light-sensitive material may contain a colorant in order to prevent halation and irradiation or to color the polymerized image. The colorant is not particularly limited, and known pigments or dyes can be used. When the colorant is used for the purpose of preventing halation or coloring the image, it is preferably added to the curable layer. When it is used for the purpose of preventing irradiation, it is preferably added to the photosensitive layer. The colorant used for preventing halation and irradiation is preferably one that absorbs light in the photosensitive wavelength region of silver halide. Examples of pigments include Color Index (CI) handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" ( Known materials described in CMC Publishing, 1984) can be used. Examples of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes. Specifically, carbon black, insoluble azo pigment, azo lake pigment, condensed azo pigment, chelate azo pigment, phthalocyanine pigment,
Anthraquinone pigment, perylene and perinone pigment, thioindigo pigment, quinacridone pigment, dioxazine pigment, isoindolinone pigment, quinophthalone pigment, dyed lake pigment, azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment , And inorganic pigments. The pigment may be used without being surface-treated, or may be used after being surface-treated. The surface treatment method includes a method of surface coating resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface. Conceivable. For the surface treatment method, refer to "Properties and Applications of Metal Soap" (Koshobo), "Printing Ink Technology" (CMC Publishing, 1984).
Year) and "Latest Pigment Application Technology" (CMC Publishing, 198)
6 years). The particle size of the pigment is 0.01 μm
10 μm, more preferably 0.05 μm to 1 μm. As a method for dispersing the pigment, a known dispersion technique used for producing ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. For details, see “Latest Pigment Application Technology” (CMC Publishing, 19
1986). In addition to commercially available dyes,
Various documents, such as "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry,
Known products described in 1970) can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, and methine dyes. Dyes for preventing irradiation, which have little effect on the sensitivity of silver halide, are disclosed in JP-B-41.
-20389, 43-3504, 43-131
68 and JP-A-2-39042, and U.S. Pat. Nos. 3,970,037, 3,423,207, 2,865,752, British Patent Nos. 10,030,392 and 1,100,546.
Although the content of the colorant varies depending on its absorbance,
01 to ² g / m ² , more preferably 0.05 to 1 g / m
²

[Antifoggant, Development Accelerator, Stabilizer] In order to improve photographic characteristics, any of the layers may contain additives such as an antifoggant, a silver halide development accelerator and a stabilizer. You can Examples of these include Research Disclosure No. 17643, pages 24 to 25 (1978), azoles and azaindenes, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or JP-A-6-68.
The acetylene compounds described in 2-87957 can be mentioned. The amount of these used is in the range of 10 ^-7 to 1 mol per mol of silver halide.

[Development Stopping Agent] In the light-sensitive material, a development stopping agent can be used for the purpose of always obtaining a constant image with respect to changes in development time and development temperature. The term "development terminating agent" as used herein refers to a compound that, after proceeding properly, promptly neutralizes or reacts with a base to lower the concentration of the base in the layer to stop the development or interact with silver and a silver salt. It is a compound that stops development. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with coexisting bases upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and their precursors. For details, see JP-A-62-253.
159, Japanese Patent Application Nos. 1-72479 and 1-347.
No. 1 is described in each specification. The development terminator may be added to any layer.

[Surfactant] A surfactant can be added to any layer. As the surface active agent, a nonionic surface active agent, an anion surface active agent, a cationic surface active agent, a fluorine-containing surface active agent, or any of those known in JP-A-2-195356 can be used. Particularly, sorbitans, polyoxyethylenes, and fluorine-containing surfactants are preferable.

[Matting Agent] As the matting agent which can be contained in the overcoat layer or the image formation accelerating layer provided on the uppermost layer of the light-sensitive material, various polymer powders (for example, natural products such as starch, synthetic products such as polyethylene) are used. Polymer) is used, and the particle size is preferably in the range of about 1 to 50 μm.

[Polymerization Inhibitor] A polymerization inhibitor may be added to the curable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. As the polymerization inhibitor, known compounds can be used. Examples include nitrosamines, thioureas, thioamides, ureas, phenols, nitrobenzene derivatives and amines. Specific examples include cuperone aluminum salt, N-nitrosodiphenylamine, allylthiourea, arylphosphite,
Mention may be made of p-toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol, pyrogallol, hydroquinone and alkyl- or aryl-substituted hydroquinones.

[Image Forming Method] The light-sensitive material of the present invention is imagewise exposed to form a latent image on silver halide, and then uniformly heated (heat development) to develop the silver halide on which the latent image is formed. At the same time, the polymerizable compound in that portion (or in the portion where the latent image is not formed) is polymerized and / or the crosslinkable binder polymer is cured to form a polymerized image, and then the uncured portion (non-image portion). Are dissolved or otherwise removed from the light-sensitive material to form a polymer image on the support.

An image forming method using the light-sensitive material of the present invention will be described with reference to FIGS. Figure 2
[FIG. 3] is a schematic sectional view showing an image exposure step. As shown in FIG. 2, the silver halide 4 in the exposed portion irradiated with the light 61
3 latent images are formed. There is no change in the silver halide 44 in the unexposed area. FIG. 3 is a schematic sectional view showing the heat development step. When the entire surface of the photosensitive material is heated 62 as shown in FIG. 3, the following reactions (a) to (c) occur.

(A) Base precursor 51 releases the base The base diffuses into the photosensitive material, and each layer is placed in a basic atmosphere.

(B) The latent image in the exposed area is developed by the action of the reducing agent on the formed silver halide to form a silver image 45. As a result, radicals are formed in the exposed area from the oxidant of the reducing agent. Radicals diffuse into the curable layer.

(C) By the action of radicals, the crosslinkable polymer is crosslinked and the curable layer in the exposed area is cured 33. With this curing, the adhesiveness between the curable layer and the hydrophilic layer increases due to the affinity with the hydrophilic layer surface, the reaction with the polymerizable compound in the hydrophilic layer, and the hardening agent. On the other hand, in the curable layer 34 and the photosensitive layer in the unexposed area, except for the diffusion of some components,
There is virtually no change. FIG. 4 is a schematic sectional view showing the etching step. When the light-sensitive material of the present invention is used as a printing original plate, the etching step can be performed after peeling and removing the upper layer including the photosensitive layer, in addition to the case where this etching step is performed after thermal development. By using an etching solution, the layers other than the cured portion of the cured layer can be removed from the photosensitive material to produce a printing plate.

Image exposure is carried out using a light source that emits light having a wavelength corresponding to the spectral sensitivity (sensitizing dye) of silver halide. Examples of light sources include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, various lasers (semiconductor laser, helium neon laser, argon laser, helium cadmium laser), light emitting diodes, A CRT tube or the like is used. Generally, the exposure wavelength is preferably visible light, near-ultraviolet light, or near-infrared light, but X-rays or electron beams may be used. The exposure amount is determined by the sensitivity of silver halide, but is generally 0.01 to 100.
00 ergs / cm ² , more preferably 0.1 to 100
It is in the range of 0 erg / cm ² . When the support is transparent, it is also possible to expose through the support from the back side of the support. Thermal development involves contact with a heated object (eg, metal plate, block or roller), immersion in a heated liquid (eg, oil bath), or heating with infrared-rich lamp radiation. Can be done. The surface of the photosensitive material may be opened in the air for heating, or may be shielded from the air (for example, the surface of the photosensitive material may be brought into close contact with an object) and heated. The heating temperature is 60-2
00 ° C., more preferably 100 to 150 ° C., the heating time is in the range of 0.5 to 180 seconds, more preferably 5 to 6 seconds.
It is in the range of 0 seconds.

As described above, when a polymerization image is formed by utilizing the polymerization inhibiting action of the reducing agent or its oxidant, radicals must be uniformly generated from the polymerization initiator. When a thermal polymerization initiator is used, radicals can be generated by heating at the time of thermal development, so heating only once is required. When a photopolymerization initiator is used, it is necessary to expose the entire surface after thermal development in order to generate radicals. As the light source, a light source containing light having a wavelength absorbed by the photopolymerization initiator is used. The light source may be selected from those used for the image exposure described above. The exposure dose is about 10 ³ -1
It is in the range of 0 ⁷ ergs / cm ² . When the etching treatment is carried out after the heat development, it is carried out by immersing it in a liquid (etching liquid) capable of removing the uncured portion of the curable layer. The etching liquid may be any one that dissolves or swells the uncured curable layer, such as an organic solvent, an alkaline aqueous solution or a mixed solution thereof. As the alkaline compound, potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium metasilicate, sodium metasilicate, potassium phosphate, sodium phosphate, ammonia and amino alcohol (eg, monoethanolamine, diethanolamine, Triethanolamine). Various organic solvents may be added to the water-based etching solution, if necessary. As the organic solvent, lower alcohols and aromatic alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and phenethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol,
Examples include polyethylene glycol, cellosolves, and the above-mentioned amino alcohols as the base. Furthermore, if necessary, the etching solution contains a surfactant, a defoaming agent,
Other additives can be added. A commercially available developing solution for a printing plate can also be used. The light-sensitive material that has undergone the heat development may be directly dipped in the etching solution, or the layers other than the curable layer may be previously washed with water or mechanically peeled to be removed, and then dipped in the etching solution.

The final image can be obtained by a method other than etching. For example, the following method can be mentioned. 1. The uncured part of the curable layer is used for its adhesiveness,
Transfer to the image receiving sheet. 2. The uncured part of the curable layer is used for its adhesiveness,
A coloring substance (toner) is attached. 3. The uncured or cured portion of the curable layer is selectively dyed. The image thus obtained is used for printing plates, color proofs, hard copies, reliefs and the like. In particular, it is most preferable to use it as a printing plate, taking advantage of the high strength of the sensitivity image of the present invention.

[0056]

【Example】

Example 1 A polyethylene terephthalate film having a thickness of 200 μm was provided on one side with a matting layer containing silica particles having an average particle size of 5 μ, and on the other side, an average particle size of 15% by weight with respect to photographic gelatin. A hydrophilic layer containing 7μ of silica fine powder was applied to a thickness of 4.0μ. A curable layer was provided on the hydrophilic layer so that the dry coating amount was 1.3 g / m ² , and a photosensitive layer and an image formation promoting layer were coated thereon.

—————————————————————————————— Curable Layer Coating Solution —————— -------------- Di-penterythritol hexaacrylate 2.5 g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 83 / 17) 20% by weight propylene glycol monomethyl ether solution 37.5 g The following pigment dispersion 13.0 g Methyl ethyl ketone 74.0 g --------------------. −−−−−−−−−−−−−

----------------------------------------- Pigment Dispersion Liquid ------ ---------------------------- Chromophtal red A2B 18 g benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 12 g Cyclohexanone 30 g Propylene glycol monomethyl ether 40 g --------------------------------.

[Preparation of Silver Halide Emulsion] After adding an appropriate amount of ammonia to a container containing gelatin, potassium bromide and water and heated to 55 ° C., the pAg value in the reaction container was adjusted to 7.60. While maintaining, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridium (III) salt (10 ^-7 mol per 1 mol of silver) was added by the double jet method, and then potassium iodide was added, Monodispersed silver iodobromide emulsion grains (silver iodide content 2 mol%) having an average grain size of 0.25 μm were prepared. In these emulsion grains, 98% of the total number of grains were present within ± 40% of the average grain size. After desalting these emulsions, the pH was adjusted to 6.
2. After adjusting the pAg to 8.6, gold and sulfur sensitization was performed with sodium thiosulfate and chloroauric acid, and then 2 mol / 1 methanol solution of the following spectral sensitizing dye was added to 1 kg of emulsion. 200 cc per unit was added, and the mixture was stirred and held at 60 ° C. for 15 minutes to prepare a silver halide emulsion.

(Spectral sensitizing dye)

[Chemical 4]

[Preparation of Reducing Agent Dispersion] 10 g of the following reducing agent powder was dispersed in 90 g of a 10% by weight aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.) using a Dynomill disperser. . The particle size of the reducing agent was about 0.5 μm or less.

(Reducing agent)

[Chemical 5]

"Formation of photosensitive layer" A liquid having the following composition is coated on the curable layer and dried to give a coating amount of about 1.2.
A photosensitive layer of g / m ² was provided.

------------------------------------------ Photosensitive layer coating liquid ----- -------------------------------------- Polyvinyl alcohol (PVA-420 manufactured by Kuraray Co., Ltd .; saponification degree 79.5%) 6% by weight aqueous solution of 8.4 g of the following polymerizable compound emulsion 2.4 g of the above reducing agent dispersion 1.2 g of 0.1% by weight methanol solution of the following additives 0.8 g of the above silver halide emulsion 0 0.5 g 5% by weight aqueous solution of the following surfactant: 0.4 g water: 6.3 g ---------------------------------. −−−−−

-------------------------------------- Emulsion ---------- 25 g of a 6% by weight aqueous solution of PVA-420 and a 5% by weight aqueous solution of the following surfactants 0: ---------------------------- A product obtained by adding 3.0 g of dipentaerythritol hexaacrylate to a mixture of 4 g and emulsifying with a homogenizer. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

(Additive)

[Chemical 6]

(Surfactant)

[Chemical 7]

[Preparation of Base Precursor Dispersion] 250 g of the powder of the following base precursor was dispersed in 750 g of a 3% by weight aqueous solution of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) using a Dynomill disperser. . The particle size of the base precursor was about 0.5 μm or less.

(Base precursor)

Embedded image

[Formation of image formation promoting layer] Next, a liquid having the following composition is coated on the above-mentioned photosensitive layer and dried to form an image forming promoting layer having a coating amount of about 3.3 g / m ^2. To prepare a photosensitive material (printing original plate).

---------------------------------------- Image forming promotion layer coating liquid ----- -------------------------------------- Polyvinyl alcohol (PVA-110 manufactured by Kuraray Co., Ltd .; saponification degree 98.5% 10% by weight aqueous solution 20.0 g of the above base precursor dispersion liquid 1.25 g 5% by weight aqueous solution of the above surfactant 4.0 g ------------------. -----------------

"Image formation and evaluation" A step wedge was brought into close contact with the above-mentioned printing original plate, and a 1-second exposure was carried out using a 500 W tungsten lamp through a band-pass filter for passing a light of 500 nm. Then the support surface is 1
After closely adhering to the surface of the hot plate heated to 40 ° C. (the surface of the image formation promoting layer is open to the air) and performing heat development, it is washed with water to remove the photosensitive layer and the image forming promotion layer, and an etching solution is used. (Fuji PS developer DN-3 manufactured by Fuji Photo Film Co., Ltd.
Upon immersion in C) at room temperature for 1 minute, etching and washing with water, the curable layer in the unexposed area was eluted and removed, and a relief image of a polymer colored red was formed in the exposed area. When this sample (printing plate) was mounted on a Hamada 611XLA-II printing machine and printed, a good printed matter with little background stain was obtained.

Example 2 A curable layer and a photosensitive layer were prepared in the same manner as in Example 1 except that a gelatin layer containing no silica fine powder was coated on the hydrophilic layer of Example 1 to a thickness of 0.5 μm. The image formation promoting layer was applied to prepare a material. A printing plate was prepared by treating in the same manner as in Example 1, mounted on a Hamada 611XL-II printing machine and printed, and a good printed matter with less background stain was obtained.

Example 3 A gelatin layer on the hydrophilic layer of Example 2 had an average particle size of 0.1.
A printing plate was prepared in the same manner as in Example 2 except that μ fine silica powder was contained. This plate is Hamada 611XL
-II When mounted on a printing machine and printed, a good printed matter with less background stain than the plate of Example 2 was obtained.

Example 4 A printing plate was prepared in the same manner as in Example 2 except that 0.2 μm of TiO ₂ fine powder was added to the hydrophilic layer of Example 2 in an amount of 5% of silica. When this printing plate was mounted on a Hamada 611XL-II printing machine and printed, a good printed matter with less background stain than the printing plate of Example 2 was obtained.

Example 5 Instead of heat-developing the sample of Example 1 and then washing with water to remove the photosensitive layer and the image formation promoting layer, peeling was carried out.
After removing the layer on the curable layer, a polymer relief image was formed with an etching solution as in Example 1 to prepare a plate material. When this plate material was attached to a Hamada 611XLA-II printing machine and printed, a good printed matter with less background stain than that of Example 1 was obtained.

[Brief description of drawings]

FIG. 1 shows a sectional view of an example of a lithographic printing material of the invention.

FIG. 2 shows a state in which the lithographic printing material shown in FIG. 1 is exposed.

FIG. 3 shows a state in which the entire surface is heated after the exposure shown in FIG.

4 shows a cross-sectional view of a printing plate obtained from the planographic printing material of FIG.

[Explanation of symbols]

 1. Support 2. Hydrophilic layer 3. Curable layer 4. Photosensitive layer 5. Image formation promoting layer 21. Hydrophilic polymer 22. Matting agent 31. Crosslinkable polymer 32. Polymerizable compound 33. Cured polymer 34. Unhardened part 41. Silver halide 42. Reducing agent 43. Exposed silver halide 44. Unexposed silver halide 45. Developed silver 51. Base precursor 61. Light 62. heat

Claims (4)

[Claims] 1. A support having at least one hydrophilic layer on which at least one curable layer containing a polymerizable compound and / or a crosslinkable polymer and a photosensitive layer containing silver halide are provided. A lithographic printing material characterized by: 2. The lithographic printing material according to claim 1, wherein the hydrophilic layer contains a hardenable polymer. 3. The hydrophilic layer has an average particle size of 0.1 to 10 μm.
2. The lithographic printing material according to claim 1, which contains the fine particle powder of. 4. The lithographic printing material according to claim 1, which further comprises an image formation promoting layer on the photosensitive layer.