JPH07219233A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which can be developed with heat in the open air and produces no sludge in a processing liquid since the overcoating layer or the photosensitive layer after heat development is soluble with water by providing an overcoating layer containing a specified PVA on a phtosensitive and polimerizable layer. CONSTITUTION:One or more photosensitive polymerizable layers containing silver halide, reducing agent, polymerizable compd., in a separated or mixed state, on a supporting body. Further, an overcoating layer is formed on the photosensitive polymerizable layer. The overcoating layer contains polyvinyl alcohol having acid residues or salt of acid residues in the molecule. Namely, acid residues are introduced into polyvinyl alcohol to prevent crystallization of polyvinylalcohol at a high temp. Thus, the polyvinyl alcohol with, has high solubility to water even after heated. The low permeability for oxygen of the polyvinyl alcohol is not decreased by introduction of acid residues.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material which utilizes the photosensitivity of silver halide to cure a polymerizable compound to form a polymer image.

[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. However, Japanese Patent Publication No. 45-11149 (US Pat. No. 3,697,275, West German Patent 172).
0665 and British patent 1131200)
It is described in. In this method, polymerization is initiated by an oxidizing radical of a reducing agent that has reduced silver halide (which may be a radical generated by decomposition of an oxidizing form of the reducing agent; hereinafter, simply referred to as oxidizing radical). .

On the other hand, a method of developing a silver halide by heating and forming a polymer image only by dry processing is disclosed in JP-A-61-69062 and 61-73145 (US Pat. No. 4,629,676 and European Patent Publication). No. 0174634A, each specification).

In the light-sensitive material used in the image forming method as described above, the silver halide, the reducing agent and the polymerizable compound are essential components in the light-sensitive material, and the light-sensitive polymerizable layer containing them is the light-sensitive material. Is an essential component of. In addition, in this specification, a polymerizable compound means a polymerizable monomer or a crosslinkable polymer. Further, the photosensitive polymerizable layer in the present specification is not only a photosensitive polymerizable layer having a single layer structure in which a silver halide, a reducing agent and a polymerizable compound are contained in a single layer, but also a silver halide. It also means a photosensitive polymerizable layer having a multilayer structure composed of a photosensitive layer containing it and a polymerizable layer containing a polymerizable compound. A light-sensitive material comprising a light-sensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound is described in JP-A-5-249667 (US Pat.
No. 2443 and European Patent Publication Nos. 0426192A) and 4-191856.

The photosensitive material described in JP-A-5-249667 discloses polyvinyl alcohol having a saponification degree of 70% or more as a binder for the overcoat layer or the photosensitive layer. Further, in the publication, polyvinyl alcohol having a saponification degree of 95% or more is described as the most preferable binder. As described in the same publication, polyvinyl alcohol having a high degree of saponification eliminates the effect of oxygen in the air (oxygen has a polymerization inhibiting effect), and promotes a smooth polymerization reaction in thermal development. Have. This effect is particularly remarkable when the saponification degree is 95% or more.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have further researched polyvinyl alcohol used as a binder for an overcoat layer or a photosensitive layer. As described in JP-A-5-249667, it is advantageous to use polyvinyl alcohol having a high degree of saponification in heat development. However, studies by the present inventors have revealed that polyvinyl alcohol having a high degree of saponification causes a problem in the elution process after thermal development.
When the light-sensitive material is used for producing a printing plate or a color proof, a method of washing and removing the overcoat layer or the light-sensitive layer after heat development is often used. In the removal by washing with water, the removed layer did not dissolve in the washing water and sludge sometimes occurred. This sludge was observed when highly saponified polyvinyl alcohol was used as the binder. Then, as a result of further research by the present inventor, it became clear that polyvinyl alcohol having a high degree of saponification is crystallized by heating in thermal development and is changed into a state insoluble in water.

An object of the present invention is to provide a light-sensitive material which can be heat-developed in the open air and which is water-soluble in the overcoat layer or the light-sensitive layer after heat development and does not cause sludge in the processing liquid. It is to be.

[0008]

The above-mentioned objects have been achieved by the following photographic material (1) or (2).

(1) One or more photosensitive polymerizable layers containing a silver halide, a reducing agent and a polymerizable compound together or separately are provided on a support, and the photosensitive polymerizable layer is further provided. 1. A photosensitive material having an overcoat layer provided on the above, wherein the overcoat layer contains polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule.

(2) A polymerizable layer containing a polymerizable compound and a photosensitive layer containing silver halide are sequentially provided on a support, and a reducing agent is added to the polymerizable layer or the photosensitive layer. A photosensitive material contained, wherein the photosensitive layer contains polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule.

[0011]

The light-sensitive material of the present invention is characterized by using polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule as a binder of the overcoat layer or the photosensitive layer. According to the research conducted by the present inventor, when an acid residue is introduced into polyvinyl alcohol, crystallization of polyvinyl alcohol under high temperature conditions can be prevented.
Therefore, polyvinyl alcohol introduced with an acid residue is
It has a high solubility in water even after heating. In addition, the introduction of acid residues does not impair the low oxygen permeability of polyvinyl alcohol. As a result of the above, the photosensitive material of the present invention can form a uniform and excellent image even if the surface is exposed to the air and subjected to a heat development treatment. Further, the overcoat layer or the photosensitive layer containing polyvinyl alcohol can be easily removed after the heat development.

[0012]

DETAILED DESCRIPTION OF THE INVENTION First, polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule will be described. The acid residue means an anionic group capable of releasing a proton. Examples of the acid that constitutes the acid residue include:
Mention may be made of carboxylic acids, sulphonic acids and phosphoric acids. The acid residue may form a salt with the cation. As the cation, a metal ion is preferable, and an alkali metal ion such as sodium ion is particularly preferable. The modified polyvinyl alcohol is more stable as a molecular structure when the acid residue is in a salt state than in a free state. In the production of polyvinyl alcohol used in the present invention, the acid residue or the salt of the acid residue as described above is introduced into the molecule of polyvinyl alcohol. Therefore, this polyvinyl alcohol is a kind of modified polyvinyl alcohol (modified Poval). The modified poval is described in "Poval (revised edition)" (Kobunshi Kogyokai), pages 280-285. Conventional polyvinyl alcohol is generally produced by saponifying polyvinyl acetate. The acid residue can be introduced by two methods: (1) copolymerization modification in the production of polyvinyl acetate and (2) post-modification after the production of ordinary polyvinyl alcohol.

In the copolymerization modification (1), vinyl acetate and an organic acid having an ethylenically unsaturated group (or a derivative thereof) are used.
Copolymerize with. Examples of the ethylenically unsaturated organic acid may include acrylic acid, methacrylic acid and styrene sulfonic acid. The organic acid derivative means any state of salt, ester, amide or acid anhydride. For example, ethylenically unsaturated organic acid amides such as acrylamide, methacrylamide, and N, N-dimethylacrylamide can also be used. Polyvinyl alcohol having an acid residue can be produced by saponifying a copolymer of vinyl acetate and an ethylenically unsaturated organic acid in the same manner as ordinary polyvinyl alcohol. When the organic acid is in the state of ester, amide or acid anhydride, hydrolysis occurs in this saponification treatment, and an acid residue is produced from the bond of ester, amide or acid anhydride.

In the post-modification of (2), a difunctional or higher functional acid (dibasic acid, tribasic acid, tetrabasic acid) is reacted with the hydroxyl group of polyvinyl alcohol. As a result, one of the plurality of functional groups of the acid is ester-bonded with the hydroxyl group, and the remaining acid functional group is in a free state. As the acid, a bifunctional or higher functional carboxylic acid (dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid) is preferable. A difunctional or higher functional carboxylic acid can be used in the anhydrous state. For example, maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, adipic anhydride and itaconic anhydride can be used.

The modified polyvinyl alcohol is effective in the present invention regardless of the method (1) or (2). However, the post-modification of (2) is easier to manufacture or obtain a commercial product. The modified polyvinyl alcohol preferably has a molecular weight of 3000 to 500,000. A unit of vinyl acetate may remain in the modified polyvinyl alcohol. That is, the saponification degree is 1
It need not be 00%. Further, it is difficult to produce polyvinyl alcohol having a saponification degree of 100%. However, the saponification degree is preferably 70% or more, and more preferably 90% or more. As described above, the modified polyvinyl alcohol used in the present invention is generally a copolymer composed of three types of units: (A) vinyl acetate unit, (B) vinyl alcohol unit, and (C) acid residue unit. . The arrangement of each unit in the copolymer may be a graft, but is preferably random. A preferable example of each unit is represented by the following formula.

[0016]

[Chemical 1]

The above formula (A) means a vinyl acetate unit. l is preferably 30% or less, and more preferably 10% or less of the sum (polymerization degree) of l + m + n1 (or n2). The vinyl acetate unit of (A) does not exist (even if 1 is 0),
The effect of the present invention can be obtained. Formula (B) means a unit of vinyl alcohol. Formula (C1) is a unit of an acid residue introduced by the copolymerization modification of the above (1). In formula (C1), R is a hydrogen atom, an alkyl group, a carboxylic acid group, or a salt thereof. R'is a hydrogen atom or a carboxylic acid group or a salt thereof. The alkyl group is preferably a lower alkyl group having 6 or less carbon atoms, and particularly preferably methyl. Link ¹ is q + 1
It is a valent linking group. The linking group is preferably a hydrocarbon residue. p is 0 or 1. p = 0, that is, the linking group may not be present. q is a natural number and is generally 1 or 2. Acid ¹ is an acid residue (eg, carboxylic acid group, sulfonic acid group, phosphoric acid group). M ¹ is a cation. The cation is preferably a proton or an alkali metal ion. n1 is preferably in the range of 0.1 to 20%, more preferably in the range of 0.5 to 10% with respect to the sum (polymerization degree) of l + m + n1. Specific examples of the modified polyvinyl alcohol produced by the copolymerization modification of (1) will be given below with reference to the above formulas (A), (B) and (C1).

[0018]

[Table 1]

The formula (C2) is a unit of acid residue introduced by the post-modification of (2). In Formula (C2), Link ² is a s + 1-valent linking group. The linking group is preferably a hydrocarbon residue. r is 0 or 1. r = 0, that is, no linking group is required. s is a natural number, generally 1 or 2. Acid ² is an acid residue (eg, carboxylic acid group, sulfonic acid group, phosphoric acid group). M ² is a cation. The cation is preferably a proton or an alkali metal ion. n2
Is preferably 0.1 to 20% with respect to the sum (polymerization degree) of l + m + n2, and is 0.5 to 10
It is more preferable that the range is%. (2) Specific examples of modified polyvinyl alcohol produced by post-modification,
The definitions of the above formulas (A), (B) and (C2) are cited and listed below.

[0020]

[Table 2]

A commercially available product may be used as the modified polyvinyl alcohol of the present invention. Examples of commercially available products include Kuraray Poval KM-118, KL-118, KL-31.
8, KL-506, KM-618 (manufactured by Kuraray Co., Ltd.),
Gocenar T and Gocelan L-3266 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) can be mentioned. You may use together two or more types of modified polyvinyl alcohol. The amount of the modified polyvinyl alcohol used is preferably 0.05 to 20 g / m ² and more preferably 0.1 to 10 g / m ² as the coating amount in the overcoat layer or the photosensitive layer. More preferable.

The acid-modified polyvinyl alcohol of the present invention may be used in combination with other types of polyvinyl alcohol. In the use of polyvinyl alcohol (including both the use of acid-modified polyvinyl alcohol alone and the combined use with other polyvinyl alcohol), the content of sodium acetate contained in the overcoat layer or the photosensitive layer is less than 1%. It is preferable to adjust so that. In addition, adjusting the content of sodium acetate to be less than 1% is effective even when the acid-modified polyvinyl alcohol is not used. According to the research conducted by the present inventors, when sodium acetate is present in an amount of 1% or more in the overcoat layer or the photosensitive layer of a light-sensitive material, the development of silver halide is suppressed and the silver image density is lowered. Along with this, curing of the polymerizable layer is suppressed, and the degree of curing of the polymer film is also reduced. Therefore, the resolution is lowered and the printing durability is deteriorated. Sodium acetate is present as an impurity in polyvinyl alcohol used for the overcoat layer and the photosensitive layer. It is considered that sodium acetate is mixed in the light-sensitive material mainly with the polyvinyl alcohol. Polyvinyl alcohol is synthesized by saponifying polyvinyl acetate, and this saponification reaction is usually performed by heating in a methanol solution containing sodium hydroxide. As a result, the acetic acid ester portion of polyvinyl acetate is hydrolyzed, and at the same time polynibiru alcohol is produced, acetic acid is produced as a by-product. Under the basicity of sodium hydroxide, this will be sodium acetate. The sodium acetate thus produced remains as an impurity in the polyvinyl alcohol. The amount of sodium acetate remaining changes depending on the conditions of the saponification reaction and the production conditions of polyvinyl alcohol synthesis, and finally the amount of sodium acetate contained in the light-sensitive material changes. In order to remove sodium acetate existing in polyvinyl alcohol, it can be purified by the method described below, for example. First, polyvinyl alcohol is added to methanol with a water content of 1 to 2% (about twice the amount of polyvinyl alcohol) while stirring, and the mixture is stirred at 40 to 50 ° C. for 1 to 2 hours, and polynivir alcohol is filtered off. The amount of sodium acetate can be reduced by repeating this operation several times. Although it is not clear how sodium acetate functions to deteriorate silver developability and curability, it inhibits the pH rise of the photosensitive layer in which silver halide is present during development. It is presumed that this may be due to the suppression of In addition, even if sodium acetate was separately added in an amount of 1% or more to the overcoat layer or the photosensitive layer of the light-sensitive material, a phenomenon in which silver developability and curability were deteriorated was observed. In the case of a photosensitive material having no overcoat layer, the content of sodium acetate in the photosensitive layer needs to be less than 1% based on the total weight of the photosensitive layer. It is preferably 0.7% or less, more preferably 0.5% or less. Further, in the case of a light-sensitive material having an overcoat layer, the content of total sodium acetate in these two layers needs to be less than 1% based on the total weight of the overcoat layer and the light-sensitive layer. It is preferably 0.7% or less, more preferably 0.5% or less. Next, a synthesis example and a purification example of polyvinyl alcohol will be shown. The same purification treatment can be performed on the acid-modified polyvinyl alcohol used in the present invention. [Synthesis Example 1] The polyvinyl acetate resin was saponified in the following manner to obtain polyvinyl alcohol having a saponification degree of 98%. 200 g of polyvinyl acetate (degree of polymerization: 700) was dissolved in 500 g of methanol and heated to 35 ° C. with stirring. Methanol 30 in which 30 g of sodium hydroxide is dissolved
0 g was added to this. The liquid temperature increased by 7 ° C. and a precipitate was deposited within a few minutes. The obtained precipitate was separated by filtration, and the obtained precipitate was ground with a grinder. This was washed with 5 liters of methanol and dried at 90 ° C. for 4 hours to obtain polyvinyl alcohol. The saponification degree of the obtained polynivir alcohol is 9
The content of 8% and sodium acetate was 5% by weight. "Purification Example 1" The polyvinyl alcohol obtained in Synthesis Example 1 was purified as follows. 1% hydrous methanol 2
The polyvinyl alcohol 10 obtained in Synthesis Example 1 was added to 00 g.
0 g was added and the mixture was heated with stirring at 50 ° C. for 2 hours. Then, filtration was performed to separate polyvinyl alcohol. By repeating this operation 7 times, polyvinyl alcohol having a sodium acetate content of 0.3% (saponification degree: 98%) was obtained. [Synthesis Example 2] In Synthesis Example 1, 20% sodium hydroxide was added.
Saponification degree is 85% in the same manner as in Synthesis Example 1 except that g is used.
To obtain partially saponified polyvinyl alcohol. The sodium acetate content of the partially saponified polyvinyl alcohol obtained was 7%. "Purification Example 2" The partially saponified polyvinyl alcohol obtained in Synthesis Example 2 was purified in the same manner as in Purification Example 1 to obtain a partially saponified polyvinyl alcohol having a sodium acetate content of 0.35%. By using polyvinyl alcohol having a low acetic acid content as described above, the amount of sodium acetate in the overcoat layer and / or the photosensitive layer of the light-sensitive material is adjusted to 1%.
When adjusted to be less than 1, the development of silver halide proceeds well and the silver image density increases. Further, along with this, the curing of the polymerizable layer is improved, and the curing degree of the polymer film is improved. Therefore, the resolution is improved, the reproducibility of minute points (highlights) is improved, and the printing durability is improved.

[Layer Structure of Photosensitive Material] The layer structure of the photosensitive material can be determined according to the application. However, the photosensitive polymerizable layer containing silver halide, a reducing agent and a polymerizable compound (polymerizable monomer or crosslinkable polymer) is a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound. It is preferably composed of layers. Further, an overcoat layer may be provided on the photosensitive polymerizable layer. When the overcoat layer is provided, polyvinyl alcohol having the acid residue or the salt of the acid residue is used as the binder of the overcoat layer. When the overcoat layer is not provided, polyvinyl alcohol having the acid residue or the salt of the acid residue is used as the binder of the photosensitive layer. The photosensitive material may be provided with another functional layer. Other functional layers include subbing layers, adhesive layers, release layers and back layers.

[Photosensitive Layer] The photosensitive layer contains silver halide and generates radicals by imagewise exposure and thermal development. The generated radicals diffuse and enter the polymerizable layer to cure the polymerizable layer. The thickness of the photosensitive layer is 0.1 to 2
The thickness is preferably 0 μm, more preferably 0.5 to 10 μm. [Polymerizable Layer] The polymerizable layer contains a polymerizable monomer or a crosslinkable polymer as a polymerizable compound. The polymerizable layer is cured by polymerizing or crosslinking the polymerizable compound. The thickness of the polymerizable layer is preferably 0.1 to 20 μm,
More preferably, it is 3 to 7 μm.

[Overcoat Layer] The overcoat layer has a function of protecting the light-sensitive material and preventing oxygen from entering in the air to enhance the degree of curing of the polymerizable layer. Further, the overcoat layer is a component that accelerates image formation (eg,
Base or base precursor, reducing agent, thermal development accelerator)
In addition to the protective function as an overcoat layer,
It may have a function of promoting image formation. The overcoat layer can include a matting agent. The matting agent reduces the tackiness of the surface of the photosensitive material and prevents adhesion when the photosensitive materials are stacked. The thickness of these layers is preferably 0.3 to 20 μm, and 0.5 to 10 μm.
Is more preferable.

[Adhesive Layer] When an image is formed using a toner, an adhesive layer can be provided on the photosensitive material. The adhesive layer is made of an adhesive polymer to which toner can be attached. As the polymer, natural or synthetic rubber is preferable. Examples of synthetic rubbers include isobutylene rubber, nitrile rubber, butyl rubber, chlorinated rubber, polyvinyl isobutyl ether, silicone elastomer, neoprene and copolymer rubber (eg, styrene-butadiene copolymer, styrene-isobutylene copolymer). When the synthetic rubber is a copolymer, the copolymerization method may be random, block or graft copolymerization. The thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[Release Layer] When an image is formed by transfer, a release layer can be provided on the photosensitive material. The peeling layer is easy to peel from the support and is non-tacky at room temperature, but exhibits tackiness or fusion property when heated. The release layer is
It includes an organic polymer (eg, polyvinyl acetal resin, amide resin) as a matrix. The flow softening point of the polymer used as the matrix is preferably equal to or higher than the heating temperature required for the reduction reaction of the reducing agent. The release layer preferably further contains 1% by weight or more of a fluorine-containing compound. As the fluorine-containing compound, a fluorine-containing surfactant can be preferably used. The thickness of the release layer is preferably 1.0 μm or more, and 1.4 μm
It is more preferable that the above is satisfied.

[Intermediate Layer] An intermediate layer can be provided between the layers. The intermediate layer can also function as an antihalation layer or a barrier layer. The barrier layer has a function of preventing components from moving between layers and diffusing or mixing during storage of the light-sensitive material. The material of the intermediate layer is determined according to the application. You may use the hydrophilic polymer used for a photosensitive layer and an overcoat layer. The thickness of the intermediate layer is preferably 10 μm or less.

[Support] As the material of the support, paper, synthetic paper, synthetic resin (eg, polyethylene, polypropylene,
Polystyrene laminated paper, plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg aluminum, aluminum alloy,
Zinc, iron, copper), paper or plastic film in which these metals are laminated or vapor-deposited can be used.

When the light-sensitive material is used for producing a lithographic printing plate, preferred support materials are an aluminum plate, a polyethylene terephthalate film, a polycarbonate film, paper and synthetic paper. A composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable.

The case where an aluminum plate is used as a support will be described below. The aluminum support is subjected to surface treatment such as surface roughening treatment (graining treatment) or surface hydrophilization treatment, if necessary. The surface roughening treatment is performed by an electrochemical graining method (for example, a method of graining an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte solution) and / or a mechanical graining method. (For example, a wire brush grain method of scratching an aluminum surface with a metal wire, 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. Law).

Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of alkaline agents include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of alkali treatment is preferably in the range of 20 to 100 ° C. Furthermore, it is preferable to adjust the treatment conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² .

Usually, after alkali etching, the aluminum plate is washed with an acid to remove stains (smuts) left on the surface. Preferred acids are nitric acid, sulfuric acid,
Phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid. The smut removal treatment after the electrochemical graining treatment can be carried out by a known method such as a method of contacting with sulfuric acid having a concentration of 15 to 65% by weight at 50 to 90 ° C.

The aluminum plate surface-roughened as described above can be subjected to anodizing treatment or chemical conversion treatment, if necessary. The anodizing treatment can be performed by a known method. Specifically, in an acid solution,
A direct current or an alternating current is applied to the aluminum plate to form an anodized film on the aluminum surface. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzene sulfonic acid. Anodizing conditions vary depending on the electrolyte solution used. Generally, the concentration of the electrolytic solution is 1 to 80% by weight, the temperature of the electrolytic solution is 5 to 70 ° C., and the current density is 0.5.
It is preferable that the range is from 60 to 60 amps / dm ² , the voltage is from 1 to 100 v, and the electrolysis time is from 10 to 100 seconds. Particularly preferred anodizing methods are a method of anodizing in sulfuric acid at a high current density and a method of anodizing phosphoric acid as an electrolytic bath.

After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in a sodium silicate aqueous solution). An undercoat layer may be provided on the surface of the support in order to improve the adhesion between the aluminum support and the polymerizable layer and the printing characteristics.

[Undercoat layer] As a component constituting the undercoat layer, a polymer (eg, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid); amine (eg, monoethanolamine, Diethanolamine, triethanolamine, tripropanolamine) and their hydrochlorides; monoaminomonocarboxylic acids (eg oxalates,
Phosphate, aminoacetic acid, alanine); Oxyamino acid (eg, serine, threonine, dihydroxyethylglycine); Sulfur-containing amino acid (eg, cysteine, cystine); Monoaminodicarboxylic acid (eg, aspartic acid, glutamic acid); Diaminomono Carboxylic acid (eg, lysine); Amino acid having aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine, anthranil); Aliphatic aminosulfonic acid (eg, sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (Eg,
And ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). It is also possible to use a compound in which some or all of the acid groups of the above compounds are salts (eg, sodium salt, potassium salt, ammonium salt). The above components may be used in combination of two or more.

Next, each component of the photosensitive material will be described. [Silver Halide] As silver halide, silver chloride, silver bromide, silver iodide, or any grain of silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. You can The shape of the silver halide grains is preferably cubic or tetradecahedral, but not limited to those having a regular crystal form, those having an irregular crystal form, or a composite form thereof. The anomalous crystal form has a potato shape,
Included are spherical, plate-like and plate-like crystal forms. In tabular grains, the grain size is generally 5 times or more the grain thickness.

There is no particular limitation on the grain size of the silver halide. Fine particles of 0.01 μm or less can also be used. On the other hand, large particles of about 10 μm can also be used. Regarding the grain size distribution, monodisperse grains are preferable to polydisperse emulsions. For monodisperse emulsions, see US Pat.
628, 3655394 and British Patent 1413.
No. 748 is described in each specification. The crystal structure of the silver halide grains may be uniform or may have different halogen compositions inside and outside. It may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining. Further, it may be bonded to a compound other than silver halide. Examples of compounds other than silver halide include silver rhodanide and lead oxide.

The silver halide grains may contain salts of other elements. Examples of other elements are copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg sulfur, selenium, tellurium), gold and VI.
Group II noble metals (eg, rhodium, iridium, iron, platinum, palladium) can be mentioned. The salts of these elements are
It can be added during or after the formation of silver halide grains to be contained in the grains. The specific method is
US Patents 1195432, 1951933, and 2
448060, 2628167, 295097.
No. 2, No. 3488709, No. 3737313, No. 3
772031, 4269927 and Research Disclosure (RD), Vol. 134,
No. 13452 (June 1975). Iridium ions can be introduced into silver halide grains by adding an aqueous solution of an iridium compound to the emulsion during preparation of the silver halide emulsion. Examples of water-soluble iridium compounds include hexachloroiridium (III) acid salts and hexachloroiridium (IV) acid salts. Similarly, rhodium ions may be introduced into the silver halide grains by adding an aqueous solution of a rhodium compound to the emulsion. Examples of water-soluble rhodium compounds include rhodium ammonium chloride, rhodium trichloride and rhodium chloride. The iridium compound or rhodium compound may be used by dissolving it in an aqueous solution of a halide for forming silver halide grains. Further, the aqueous solution of the iridium compound or the rhodium compound may be added before the particles are formed or may be added while the particles are formed. Further, it may be added between the grain formation and the chemical sensitization treatment. It is particularly preferred to add it while the particles are being formed. Iridium ion or rhodium ion is preferably used in an amount of 10 ^{-8 to} 10 ^-3 mol per mol of silver halide,
It is more preferable to use 10 ^{-7 to} 10 ^-5 mol. In addition, when using a rhodium compound and an iridium compound together, it is preferable that the former use is performed before the latter use.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits, and grain sizes may be used in combination. It is preferable to use silver halide as an emulsion. The silver halide emulsion is described in Research Disclosure (RD) No. 17643 (December 1978)
Mon., pp. 22-23, "I. Emulsion prepa
ration and types) ", and No. 18716 (19)
(November 1979), p.648. The silver halide emulsion is usually subjected to chemical sensitization after physical ripening, but chemical sensitization may not be performed. It is preferred to use silver halide grains having a relatively low fog value. Additives used in such processes are described in Research Disclosure, No. 17643 and No. 17643. 18716. No. for chemical sensitizers. 17643 (page 23) and No. 187
16 (page 648, right column). In addition, other known additives other than those mentioned above are
It is described in Disclosure Magazine. For example, regarding the sensitivity enhancer, No. 18716 (page 648, right column)
No. 1 for antifoggants and stabilizers. 176
43 (pages 24 to 25) and No. 18716 (Page 649, right column).

The silver halide emulsion is usually used after spectral sensitization. The sensitizing dye used in the light-sensitive material may be a silver halide sensitizing dye known in the photographic art and the like. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Along with the sensitizing dye, a dye having no spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (supersensitizer) may be added to the emulsion. Good.

[Organic Metal Salt] An organic metal salt can be added to the photosensitive layer of the light-sensitive material of the present invention together with silver halide. As such an organic metal salt, it is particularly preferable to use an organic silver salt. The organic compound used to form the organic silver salt, triazoles, tetrazoles, imidazoles, indazoles, thiazoles, thiadiazoles, azaindenes, aliphatic having a mercapto group as a substituent, aromatic or Heterocyclic compounds can be mentioned. Further, a silver salt of carboxylic acid or silver acetylene can be used as the organic silver salt.
Two or more kinds of organic silver salts may be used in combination. The organic silver salt is used in an amount of 10 ^{−5 to} 10 mol, preferably 10 ^{−4 to} 1 mol, per mol of silver halide. Further, instead of the organic silver salt, an organic compound constituting the organic silver salt is added to the photosensitive layer,
It may be converted into an organic silver salt by partially reacting with silver halide in the photosensitive layer.

[Reducing Agent] The reducing agent has a function of reducing silver halide or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols,
p-phenylenediamines, 3-pyrazolidones, 3-
Aminopyrazoles, 4-amino-5-pyrazolones,
5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o-
Or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5 -Pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles,
Included are sulfonamide pyrazolotriazoles, α-sulfonamido ketones and hydrazines.

The above reducing agents are disclosed in JP-A-61-18364.
No. 0, No. 61-188535, No. 61-228441
No. 62-70836, 62-86354, 62-86355, 62-206540, 62.
-264041, ibid. 62-109437, ibid. 63-
254442, JP-A-1-267536, 2-1.
No. 41756, No. 2-141757, No. 2-2072.
No. 54, No. 2-262662, and No. 2-269352 (including those described as a developer or a hydrazine derivative). Regarding 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-62-210
As in the light-sensitive material described in Japanese Patent No. 446, a reducing agent precursor that releases the reducing agent under heating conditions, contact with a base, or the like may be used instead of the reducing agent.

Among 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 a suitable acid. These reducing agents may be used alone, or as described in each of the above publications, two or more reducing agents may be used in combination. When two or more reducing agents are used in combination, the reducing agents interact as follows: first, to promote reduction of silver halide (and / or organic silver salt) by so-called superadditivity; Inducing polymerization of a polymerizable compound through a redox reaction with another reducing agent in which an oxidized product of the first reducing agent produced by reduction of silver halide (and / or organic silver salt) coexists. (Or suppressing polymerization) is 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 preferably used in the range of 0.1 to 10 mol, and more preferably in the range of 0.25 to 2.5 mol, per mol of silver halide.

By adjusting the kind and amount of the reducing agent, the polymerizable compound in the portion of the silver halide latent image formed portion or the portion not formed of the latent image is selectively polymerized. be able to. The reducing agent develops silver halide and is itself oxidized to an oxidant. When the oxidant of this reducing agent decomposes in the layer to generate radicals,
Polymerization occurs in the area where the latent image of silver halide is formed. Examples of such reducing agents include hydrazines. On the other hand, when the oxidant does not generate (or does not easily generate) radicals and the reducing agent itself or the oxidant has a polymerization suppressing function, it is necessary to include a polymerization initiator (radical generator) with the reducing agent. The part where the latent image of silver halide is not formed (when the oxidation inhibitor has a stronger polymerization inhibiting function than the reducing agent) or the latent image is formed (the reducing agent has a polymerization inhibiting function than the oxidizing agent) When it is strong, polymerization occurs. Examples of the reducing agent having the above function include 1-phenyl-3-pyrazolidones and hydroquinones. In this case, it is necessary to add a thermal polymerization initiator or a photopolymerization initiator as described below to the photosensitive material.

[Polymerization Initiator] Regarding the thermal polymerization initiator,
It is described in pages 6 to 18 of "Addition Polymerization / Ring-Opening Polymerization" (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science and Editorial Committee of Polymer Experiments, and JP-A-61-243449. Examples of thermal polymerization initiators include azo compounds (eg, azobis (isobutyronitrile), 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 2 , 2'-azobis (2-methylbutyronitrile), azobisdimethylvaleronitrile),
Peroxides (eg, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide,
Hydrogen peroxide, potassium persulfate, ammonium persulfate) and sodium p-toluenesulfinate may be mentioned. Regarding the photopolymerization initiator, Oster et al. “Chem
ical Review "Vol. 68 (1968), 125-15
Page 1, "Light-Sensitive System" by Kosar (John Wil
ey & Sons, 1965) pp. 158-193 and JP-A-61-75342 and JP-A-2-207254. Examples of the photopolymerization initiator include carbonyl compounds (eg, α-alkoxyphenyl ketones, polycyclic quinones, benzophenone derivatives, xanthones,
Thioxanthones, benzoins, commercially available photopolymerization initiators (eg, “Irgacure 651” and “Irgacure 907” manufactured by Ciba Geigy)), halogen-containing compounds (eg, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl) And chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones), haloalkanes, α-
Halo-α-phenylacetophenones, redox couples of photoreducible dyes and reducing agents, organic sulfur compounds, peroxides, optical semiconductors (eg, titanium dioxide, zinc oxide), metal compounds (eg, iron (I)) Salts, metal carbonyls, metal complexes, uranyl salts), silver halides, azo and diazo compounds.

Specific examples of the photopolymerization initiator include 2-dimethoxy-2-phenylacetophenone and 2-methyl- {4-.
(Methylthio) phenyl} -2-morpholino-1-propanone, benzoin butyl ether, benzoin isopropyl ether, benzophenone, Michler's ketone,
4,4′-diethylaminobenzophenone, chloromethylbenzophenone, chlorosulfonylbenzophenone,
9,10-anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9,10-phenanthrenequinone, xanthone, chloroxanthone, thioxanthone, chlorothioxanthone, 2,4 -Diethylthioxanthone, chlorosulfonylthioxanthone, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, fluorene and carbon tetrabromide. The polymerization initiator is per 1 g of the polymerizable compound,
It is preferably used in the range of 0.001 to 0.5 g, and more preferably 0.01 to 0.2 g.

[Polymerizable Compound] As the polymerizable compound,
Polymerizable monomers or crosslinkable polymers can be used. The polymerizable monomer and the crosslinkable polymer may be used in combination. Examples of the polymerizable monomer include compounds having addition polymerization or ring-opening polymerization. The compound having an addition polymerizable property includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable property includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. Examples of the compound having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters. , Itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and derivatives thereof. Acrylic acid esters or methacrylic acid esters are preferred.

Specific examples of acrylic acid esters include:
n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexane Diol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, tricyclodecane dimethylol diacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A, 2,2-dimethyl-3-
Diacrylate of a condensate of hydroxypropionaldehyde and trimethylolpropane, 2,2-dimethyl-3
A triacrylate of a condensate of hydroxypropionaldehyde and pentaerythritol, a diacrylate of polyoxyethylenated bisphenol F, a polyurethane acrylate, a polyethylene glycol diacrylate,
Polypropylene diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-
5-ethyl-1,3-dioxane diacrylate, 2-
(2-hydroxy-1,1-dimethylethyl) -5,5
Mention may be made of dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

Specific examples of the methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate. And a compound obtained by substituting a part or all of the acryloyl group of the polymerizable monomer compound mentioned as a specific example of the above acrylic acid esters such as dimethacrylate of polyoxyalkylenated bisphenol A with a methacryloyl group.

As the crosslinkable polymer, any known polymer having a radical-reactive group can be used. These polymers may be homopolymers or copolymers with monomers that do not have groups reactive with radical species. Such a polymer is a polymer having a double bond group (A) in the main chain or side chain of a molecule to which a radical (a polymerization initiation radical or a growth radical in a polymerization process of a polymerizable monomer) can be added. And (B) main chain or side chain atoms (hydrogen atom, halogen atom such as chlorine) due to radicals
Is a polymer that is easily extracted to generate a polymer radical. Examples of the above-mentioned polymer (A) include polymers having an ethylenically unsaturated double bond in the side chain as described in JP-A No. 64-17047 (eg,
Allyl (meth) acrylate polymers (including copolymers), 1,2-polybutadiene, 1,2-polyisoprene) and polymers having unsaturated double bonds in the main chain (eg, poly-1,4-butadiene, poly) Mention may be made of -1,4-isoprene (including copolymers), natural and synthetic rubbers. As an example of the above-mentioned polymer of (B), "polymer reaction" (Polymer Society of Japan, Kyoritsu Shuppan, 19
The polymers described on pages 147 to 192 of 1978) can be mentioned. Specifically, poly (meta)
Acrylate, polyvinyl butyrate, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl acetate, polyvinylidene chloride, vinyl acetate-ethylene copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene, chlorinated polypropylene, polycarbonate, diacetyl cellulose, cellulose acetate butyrate Rate, triacetyl cellulose, ethyl cellulose,
Examples thereof include polyvinyl pyridine and polyvinyl imidazole. As described below, when the etching treatment is performed with an alkaline aqueous solution after the polymerization, the crosslinkable polymer preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups,
Examples thereof include acid anhydride groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups and sulfonimide groups. Specific examples include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. For copolymers,
The molar content of the monomer having an acidic group is in the range of 1 to 50%, more preferably 5 to 30%.

Two or more kinds of the above-mentioned polymerizable compounds may be used in combination. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent or the coloring agent can also be used as the polymerizable compound. As described above, the use of a substance that also serves as a reducing agent and a polymerizable compound or a coloring agent and a polymerizable compound is also included in the aspect of the light-sensitive material. The polymerizable compound is contained in the polymerizable layer in an amount of preferably 3 to 90% by weight based on the total amount of the layer, and 15 to 6
It is more preferable that the content is 0% by weight.

[Binder of Polymerizable Layer] The polymerizable layer contains
Further binders can be added to improve the strength. As the binder, natural and synthetic polymer compounds can be used. When a crosslinkable polymer is used as the polymerizable compound, the crosslinkable polymer functions not only as the polymerizable compound but also as the binder. Specific examples of binders include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), polycondensation type synthetic homopolymers and copolymers (eg, polyesters, polyamides, polyurethanes, Polyester-polyamide). When the etching treatment is carried out with an alkaline aqueous solution after the polymerization, the polymer used as the binder preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups and sulfonimide groups. Specific examples include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. In the case of a copolymer, the molar content of the monomer having an acidic group is preferably 1 to 50%, more preferably 5 to 30%. As the polymer used for the binder, a crosslinkable polymer having an acidic functional group in its molecule is particularly preferable. An example of such a polymer is a copolymer of allyl (meth) acrylate and (meth) acrylic acid. When a polymer having an ethylenically unsaturated double bond in the side chain is used as the binder or the polymerizable compound, an image can be obtained even if the polymerizable layer does not contain a polymerizable monomer. It is preferable to use a monomer in combination because the hardness can be increased. Further, an image can be obtained even when the polymerizable layer does not contain a binder but contains only the polymerizable monomer, but when the polymerizable monomer is a liquid, the polymerizable layer becomes too soft, which is not preferable. The amount of the binder added to the polymerizable layer is generally 80% by weight or less, preferably 70% by weight, based on the entire polymerizable layer.
It is the following.

[Base or Base Precursor] The light-sensitive material may contain a base or a base precursor.
In particular, in the case of performing dry development processing by heating, the light-sensitive material preferably contains a base or a base precursor. As the base and the base precursor, inorganic bases and organic bases, or base precursors thereof (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. Examples of inorganic bases are described in JP-A-62-209448. Examples of organic bases include tertiary amine compounds (described in JP-A-62-170954), bis- or tris-, or tetra-amidine compounds (JP-A-6-16065).
3-316760) and bis or tris or tetraguanidine compounds (JP-A-64-68).
746). In the present invention, a base having a pKa of 7 or higher is preferred. In the present invention, a base precursor is preferable to a base from the viewpoint of storage stability of the light-sensitive material. Examples of preferable base precursors include salts of organic acids and bases that are decarboxylated by heating (JP-A-63-316760, 64-68746, 5).
Nos. 9-180537 and 61-313431) and urea compounds that release a base upon heating (described in JP-A-63-96159). As a method of releasing a base by utilizing a reaction, a reaction with a transition metal acetylide or a salt containing an anion having an affinity higher than that of the acetylide anion for the transition metal ion (described in JP-A-63-25208) Or
A basic metal compound which is sparingly soluble in water and a compound capable of complexing with a metal ion constituting the basic metal compound in water as a medium are contained, and a reaction between these two compounds in the presence of water. And a method of releasing the base (described in JP-A-1-3282). The base precursor of the present invention preferably releases a base at 50 ° C to 200 ° C, and more preferably releases a base at 80 ° C to 160 ° C. The base and the base precursor can be used in combination. The base or base precursor is preferably used in the range of 0.1 to 20 mol per mol of silver halide,
The range is more preferably 0.2 to 10 mol.

[Heat Development Accelerator] The light-sensitive material used in the present invention may contain a heat development accelerator in any layer in order to accelerate heat development and to carry out heat development processing in a shorter time. .
The thermal development accelerator may be a compound having a plasticizing action at room temperature or upon heating with respect to the binder used in any layer of the light-sensitive material, or a compound having no plasticizing action but capable of being melted in the layer by heating. Any of these can be used. As the compound having a plasticizing effect on the binder used in any layer of the light-sensitive material at room temperature or at the time of heating, all known compounds known as plasticizers for polymer compounds can be used. As such a plasticizer, "Plastic compounding agent" Taiseisha, P21-63;
"Plastics Additives 2nd Edition" (Plastics
Additives, 2nd Edition) Hanser Publishers, Chap.
5 P251-296; "Thermoplastic Additives"
(Thermoplastics Additives) Marcel Dekker Inc. Cha
p.9 P345-379; “Plastics Additives A Industrial Guide” (Plastics Additives A
n Industrial Guide) Noyes Publications, Section-14
P333-485; "The Technology of Solvents.
And Plasticizers "(The Technology of
Solvents and Plasticizers) John Wiley & Sons Inc.
Chap.15 P903-1027); "Industrial Plasticizers, Pergamon"
Press); "Plasticizer Technology No. 1
Volume "(Plasticizer Technology Vol.1, Reinhold Publi
shing Corp.); "Plasticization and Plasticizer Process" (Plusticization a
The plasticizers described in nd Plusticizer Process, American Chemistry) can be used. Preferred thermal development accelerators are glycols (eg, diethylene glycol, dipolypropylene glycol), polyhydric alcohols (eg, glycerin, butanediol, hexanediol), sugars,
Formic acid esters, ureas (eg, urea, diethylurea, ethyleneurea, propyleneurea), urea resins, phenol resins, amide compounds (eg, acetamide, propionamide), sulfamides and sulfonamides can be mentioned. Further, two or more of the above thermal development accelerators can be used in combination. It is also possible to add it by dividing it into two or more layers. The addition amount of the thermal development accelerator is preferably 0.05 to 2 g / m ² ,
It is more preferably 0.1 to 1 g / m ² .

[Colorant] A colorant may be added to the light-sensitive material for the purpose of preventing halation and irradiation or coloring the polymerized image. As the colorant for this purpose, any known colorant regardless of pigment or dye may be used as long as it does not significantly hinder the polymerization and curing reaction of the polymerizable layer, or does not significantly hinder the photosensitivity and developability of the silver halide. Can be used. When the colorant is used for the purpose of preventing halation or coloring the image, it is preferably added to the polymerizable layer. Further, when it is used for the purpose of preventing irradiation, it is preferably added to the photosensitive layer. When a coloring agent is added to prevent halation and irradiation, it is preferable that the coloring agent can absorb light in the photosensitive wavelength region of silver halide. As a pigment that can be used as a colorant, commercially available pigments and color index (CI) handbooks, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest pigment application technology" (CMC Publishing) , 1986) and "Printing Ink Technology" (CMC Publishing, 1984). Examples thereof 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, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments. A quinophthalone pigment, a dyed lake pigment, an azine pigment, a nitroso pigment, a nitro pigment, a natural pigment, a fluorescent pigment, and an inorganic pigment can be used. These pigments may be used without being surface-treated, or may be used after being surface-treated. The surface treatment method includes a method of coating a surface of 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. The above-mentioned surface treatment method is described in "Characteristics and Applications of Metal Soap" (Koushobo), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 198).
6 years). The particle size of the pigment is preferably in the range of 0.01 to 10 μm, and 0.05 to 1
More preferably, it is in the range of μm. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. As the disperser, ultrasonic disperser, sand mill, attritor, pearl mill, super mill, ball mill, impeller, disperser,
A KD mill, a colloid mill, a dynatron, a three roll mill, a pressure kneader and the like can be mentioned. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986). As the dye that can be used as the colorant, commercially available dyes and known dyes described in the literature (for example, “Handbook of Dyes” edited by the Society of Organic Synthetic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes,
Examples include dyes such as methine dyes. Dyes for prevention of irradiation that have little effect on the sensitivity of silver halide are
Japanese Patent Publication Nos. 41-20389, 43-3504, and 4
No. 3-13168 and Japanese Patent Laid-Open No. 2-39042, and US Pat. Nos. 3697037 and 342320.
7, No. 2865752, British Patent Nos. 1030392 and 1100546. The amount of the colorant used is 0.01 to 2 g / m ² , more preferably 0.05 to 1 g / m ² .

[Antifoggant, Development Accelerator, Stabilizer] In order to improve photographic characteristics, additives such as an antifoggant, a silver development accelerator that promotes silver development, and a stabilizer are contained in any layer. You may let me. 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, 62-879.
The acetylene compounds described in JP-A-57 can be mentioned. The amount of these compounds used is in the range of 10 ^{-7 to} 1 mol per mol of silver halide.

[Development Stopping Agent] In the present invention, various development stopping agents can be used for the purpose of always obtaining a constant image with respect to the processing temperature and the processing time during heat development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the layer to stop development after proper development, or inhibits development by interacting with silver and a silver salt. It is a compound that causes. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. Regarding the thermal development stopper, see JP-A-62-2531.
59, JP-A-2-42447 and 2-26.
It is described in each publication of 2661.

[Surfactant] In the present invention, a surfactant can be added to any layer. Known surfactants can be used as the surfactant. Examples include nonionic activators, anionic activators, cationic activators, fluorine activators, and the surfactants described in JP-A-2-195356. In particular, sorbitans, polyoxyethylenes, and nitrogen-containing surfactants are preferable.

[Matting Agent] The matting agent which can be contained in the back layer of the light-sensitive material or the overcoat layer provided on the uppermost layer on the side coated with the light-sensitive layer is used in the general field of silver salt photography. Discontinuous solid particles of an inorganic or organic material dispersible in the well known hydrophilic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide), alkaline earth metal salts (eg, barium sulfate, strontium sulfate, magnesium sulfate, potassium carbonate), images Mention may be made of silver halide grains and glasses which do not form. Further, examples of the organic matting agent include starch, cellulose ester, cellulose ether and synthetic resin. As the synthetic resin, it is preferable to use a water-insoluble or poorly water-soluble synthetic polymer. Examples of such polymers include homopolymers or copolymers of alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, glycidyl acrylates, glycidyl methacrylates, acrylamides, methacrylamides, vinyl esters, acrylonitriles, olefins, styrenes or benzoguanamines. included. In the case of the above copolymer, examples of other copolymerized units include acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate and styrene sulfonic acid. Can be mentioned. In addition, epoxy resin, nylon, polycarbonate, phenol resin,
Polyvinylcarbazole and polyvinylidene chloride can also be used. Further, an alkali-soluble matting agent such as an alkyl methacrylate / methacrylic acid copolymer (Japanese Patent Laid-Open No. 53-
No. 7231, No. 58-66937 and No. 60-88
94) and alkali-soluble polymers having anionic groups (described in JP-A-58-166341).
Is also available. The particle size of the matting agent is preferably in the range of 1 to 50 μm. The particle size distribution may be monodisperse or polydisperse. A matting agent having a maximum particle size of not more than 30 μm and having a particle size of 20 μm or more is particularly preferably 10 vol.% Or less. The amount of the above matting agent used is preferably in the range of 0.01 to 1 g / m ² , and more preferably in the range of 0.1 to 0.7 g / m ² .

[Polymerization Inhibitor] A polymerization inhibitor may be added to the polymerizable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. As the polymerization inhibitor for this purpose, any conventionally known polymerization inhibitor can be used. Examples of the polymerization inhibitor include nitrosamine compounds, thiourea compounds, thioamide compounds, urea compounds, phenol derivatives, nitrobenzene derivatives and amine compounds. More specifically, cuperone aluminum salt, N-nitrosodiphenylamine, allylthiourea, aryl phosphite, p
-Toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol, pyrogallol, hydroquinone, and alkyl- or aryl-substituted hydroquinone.

Each process of image formation will be described below. [Image exposure processing] Image exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity (sensitizing dye) of silver halide. Examples of light sources that can be used include tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps and other lamps, various lasers (eg, semiconductor lasers,
Examples thereof include a helium neon laser, an argon ion laser, a helm cadmium laser), a light emitting diode, and a cathode ray tube. The exposure wavelength is generally 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 10000 ergs / cm.
² , more preferably 0.1 to 1000 erg / cm ²
Is the range. When the support is transparent, it is also possible to expose through the support from the back side of the support.

[Heat Development Processing] The heat development is carried out by a method of bringing the light-sensitive material into close contact with a heated object (eg, metal plate, block, roller), immersing it in a heated liquid, or irradiating infrared rays. You can The surface of the light-sensitive material may be opened to the air and heated from the support side.
The heating temperature is in the range of 60 to 200 ° C, more preferably 100 to 150 ° C. Heating time is 1 to 180 seconds,
More preferably, it is in the range of 5 to 60 seconds. The exposed photosensitive material may be preheated at a temperature lower than the main heating condition or at a short time, or may be postheated after the main heating. The post-heating may be performed after the image formation post-treatment, for example, after the elution (etching) treatment.

When the oxidant radical of the reducing agent initiates the polymerization, the above heating forms a polymer image.
When a polymerization image is formed by utilizing the polymerization inhibiting action of the reducing agent or its oxidant, it is necessary to uniformly generate radicals from the polymerization initiator. When using a thermal polymerization initiator,
Since the radicals can be generated by heating during the heat development, the heating may be performed once. When a photopolymerization initiator is used,
In order to generate radicals, it is necessary to expose the entire surface after thermal development. The light at this time must have a wavelength that can be absorbed by the photopolymerization initiator. The light source can be appropriately selected from those exemplified as the light source used for the image exposure. Exposure dose is 10 ^{3 to} 10 ⁷
It is in the range of ergs / cm ² .

After heat development, the resulting image has a chemical or physical property (for example, solubility, surface tackiness, adhesion strength with the support, softening point, etc.) between its cured and uncured areas. Post-treatment is performed by utilizing the difference in refraction, dielectric constant, diffusivity, and colorability. As post-treatment, elution (etching) treatment,
Examples include removal processing (by sheet), transfer processing, toner development processing and dyeing processing. Hereinafter, each process will be described. You may implement combining these processes arbitrarily.

[Elution Process] In the elution process, the difference in solubility between the uncured portion and the cured portion is utilized to elute only the uncured portion to form a polymer image. Usually, the photosensitive material is immersed in a liquid (etching liquid) capable of removing the uncured portion. As the etching liquid, a liquid that dissolves or swells the uncured polymerizable layer, such as an organic solvent, an alkaline aqueous solution, or a mixed solution thereof, is used. Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium metasilicate, sodium metasilicate, potassium phosphate, sodium phosphate, ammonia and amino alcohols (eg, monoethanolamine, diethanolamine). , Triethanolamine). Various organic solvents may be added to the water-based etching solution, if necessary. Examples of organic solvents include lower alcohols (eg, methanol, ethanol, propanol, butanol), aromatic ring-containing alcohols (eg, benzyl alcohol, phenethyl alcohol),
Mention may be made of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and the amino alcohols mentioned above as bases. Further, a surfactant, a defoaming agent, and other additives can be added to the etching solution as needed. Further, a commercially available developing solution for a printing plate can also be used. The photosensitive material that has undergone the heat development may be directly immersed in the etching solution, or may be previously immersed in the etching solution after the photosensitive layer other than the polymerizable layer is washed with water or peeled and removed. .

[Removal Treatment] The removal by the sheet utilizes the difference in the adhesive strength between the uncured portion and the support of the cured portion to selectively remove the uncured portion or the cured portion from another sheet (removal sheet). ) And carry out. As a result, the portion remaining on the photosensitive material is used as an image. The removal sheet is
It may be laminated with a light-sensitive material before image exposure or development.

[Transfer Processing] In the transfer processing, the uncured portion or the cured portion is selectively separated into another sheet (image receiving material) by utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion. It is attached to and transferred. As a result, the portion transferred to the image receiving material is used as an image. The image receiving material may be laminated with the photosensitive material before image exposure or development. Further, the toner image obtained may be transferred by first performing the following toner development processing.

[Toner Development Processing] A coloring substance (toner) is selectively adhered to the uncured portion or the cured portion to visualize the image. It is also possible to provide an adhesive layer on the photosensitive material, selectively remove the uncured portion or the cured portion, and then attach the toner to the exposed adhesive layer. further,
The toner developing process can be performed on the image receiving material to which the uncured portion or the cured portion is selectively transferred.

[Dyeing Process] The uncured part or the cured part is selectively dyed to visualize the image. The dyeing process may be performed on the image receiving material to which the uncured portion or the cured portion is selectively transferred.

The image obtained as described above can be used for printing plates, color proofs, hard copies, reliefs and the like.

[0073]

[Example] [Example 1] Preparation of photosensitive material " Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the aluminum plate according to S-A-1050 was grained with a nylon brush and an aqueous suspension of pumicetone (400 mesh), and then thoroughly washed with water. Next, 10%
It was immersed in the aqueous solution of sodium hydroxide for 30 minutes at 70 ° C. for etching, and then washed with running water. It was neutralized and washed with a 20% nitric acid aqueous solution, and then washed with water. The obtained aluminum plate was subjected to alternating rectangular wave current (conditions: voltage at anode 12.7 v, ratio of electricity at cathode to electricity at anode: 0.9, electricity at anode: 160 coulomb / dm ² ).
With 1% containing 0.5% aluminum nitrate
Electrolytic surface roughening treatment was performed in a nitric acid aqueous solution. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Following this treatment, it was immersed in a 1% aqueous sodium hydroxide solution at 40 ° C. for 30 minutes, and then treated in a 30% aqueous sulfuric acid solution at 55 ° C. for 1 minute. Next, in a 20% aqueous solution of sulfuric acid, anodization treatment was performed under a condition of electric density of 2 A / dm ² using direct current so that the thickness became 2.5 g / dm ² .
It was washed with water and dried to prepare an aluminum support.

"Formation of Undercoat Layer" A 0.02 wt% silver nitrate aqueous solution was applied to the above support by a whiler (200 rp).
m) and dried at 100 ° C. for 1 minute to form an undercoat layer.

[Formation of Polymerizable Layer] The following coating liquid was applied onto the undercoat layer and dried to form a polymerizable layer having a thickness of 1.3 μm.

──────────────────────────────────── Polymerizable layer coating liquid ────── ────────────────────────────── Pentaerythritol tetraacrylate 0.23g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio = 80/20) 0.50 g Pigment dispersion liquid below 4.47 g 0.56 wt% methanol solution of the following additives 0.56 g Surfactant (Megafac F176PF, manufactured by Dainippon Ink and Chemicals, Inc.) 0 ． 3% by weight aqueous solution 1.00 g methyl ethyl ketone 0.62 g propylene glycol monomethyl ether 2.50 g ──────────────────────────────── ────

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Pigment (Chromophtal red A2B, Ciba Geigy) 6.90 g Allyl methacrylate / methacrylic acid copolymer (Copolymerization molar ratio = 80/20) 5.73 g Cyclohexanone 12.90 g Propylene glycol monomethyl ether 74.47 g ─────────────────────────── ──────────

[0078]

[Chemical 2]

[Preparation of Silver Halide Emulsion] The following thioether compound was added to a container containing gelatin, potassium bromide, and water and heated at 55 ° C. in an amount of 2.0 × with respect to the amount of silver nitrate added.
It was added in an amount corresponding to 10 ^-3 mol. While maintaining the pAg value of the reaction vessel at 9.2, the molar ratio of rhodium to the total amount of silver nitrate aqueous solution and potassium iodide and silver nitrate was 4 ×.
An aqueous potassium bromide solution containing rhodium ammonium chloride in an amount of 10 ^-8 mol was added by the pAg control double jet method to form silver iodobromide grains. Further subsequently, at the same temperature, pAg = 8.
At 9, the aqueous solution of silver nitrate and hexachloroiridium (I) were added so that the molar ratio of iridium to silver was 10 ^-7 mol.
II) The potassium bromide solution to which the acid salt was added was added in two stages by a double jet method to prepare a core / shell type silver iodobromide emulsion having the following composition.

[0080]

[Chemical 3]

Core: silver iodobromide (silver iodide content: 7.5 mol%) Shell: pure silver bromide Core / shell: 3/7 (silver mol ratio) Average silver iodide content: 2.3 Mol% Average particle size: 0.28 μm

The resulting emulsion grains were monodisperse, and 98% of all grains were present within ± 40% of the average grain size. Next, after desalting this emulsion, 200 ml of a methanol solution of the following spectral sensitizing dye (10 ^-2 M / liter) was added to an emulsion corresponding to 1 mol of silver nitrate, and the pH was 6.2 and pAg was adjusted. Adjusted to 8.7. Furthermore, gold and sulfur sensitization was performed using sodium thiosulfate and chloroauric acid,
A silver halide emulsion was prepared.

[0083]

[Chemical 4]

"Preparation of mercapto silver compound" Polyvinyl alcohol (PVA-420, manufactured by Kuraray Co., Ltd.) 2.8
g was dissolved in 60 g of water, 10.3 g of 0.1N potassium hydroxide aqueous solution was added, and the mixture was heated to 50 ° C. While stirring
An aqueous solution containing 0.93 mmol of silver nitrate and a methanol solution containing 0.93 mmol of the following mercapto compound were simultaneously added dropwise to this solution over 20 minutes, and the mixture was stirred for 20 minutes after the completion of the addition. Then, after cooling to room temperature, pH
Was adjusted to 6.3. In this way, a mercapto silver compound in which -SH of the following mercapto compound was converted to -SAg was prepared. The yield was 113.68g. Also,
The pAg of the solution of this compound was 6.31.

[0085]

[Chemical 5]

[Formation of Photosensitive Layer] The following coating solution was prepared, coated on the polymerizable layer and dried to form a photosensitive layer having a dry film thickness of about 1.2 μm.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol (trade name: PVA-405, Kuraray Co., Ltd.) 5.23 g 5% by weight aqueous solution of the surfactant of 1.68 g, 10% by weight aqueous dispersion of the following reducing agent 10.08 g Phosphate buffer (KH ₂ PO ₄ : 0.025 mol / liter + Na ₂ HPO ₄ : 0.025 mol / Liter) 1.68 g 0.5% aqueous solution of potassium bromide 2.10 g 0.11% aqueous solution of the above mercapto silver compound 3.20 g The above silver halide emulsion (4.3 times diluted with water) 18.48 g Water 47.69g ──────────────────────────── ────────

[0088]

[Chemical 6]

[0089]

[Chemical 7]

[Preparation of Base Precursor Dispersion] 250 g of the powder of the following base precursor was added to polyvinyl alcohol (P of Kuraray Co., Ltd.) using a Dynomill disperser.
It was dispersed in 750 g of a 3% by weight aqueous solution of VA-205).

[0091]

[Chemical 8]

[Formation of Overcoat Layer] The following coating solution was prepared, coated on the photosensitive layer and dried to form an overcoat layer having a dry film thickness of about 3.7 μm.

──────────────────────────────────── Overcoat layer coating liquid ────── ────────────────────────────── 15.0g Polyvinyl alcohol shown in Table 1 below 15.0g of the above base precursor dispersion 5% by weight aqueous solution of the above-mentioned surfactant 3.00 g water 135.0 g ────────────────────────────────── ───

(Image formation) The light-sensitive material was exposed at 3 lux for 3 seconds using a 500 W tungsten lamp and a band-pass filter that passed light of 500 nm.
Next, the back surface (the surface on the side of the support) of the photosensitive material was pressed against a hot plate heated to 145 ° C. to heat it. After removing the photosensitive layer and the overcoat layer by washing with water, the polymerizable layer was etched using an alkaline aqueous solution (DP-4 manufactured by Fuji Photo Film Co., Ltd. diluted 1/8). The light-sensitive material was thoroughly washed with water to form a polymer relief image on the exposed portion of the polymerizable layer.

(Evaluation of Water Solubility of Image and Overcoat Layer) The solubility of the image and the overcoat layer prepared as described above in water was evaluated. The results are shown in Table 1.

[0096]

[Table 3] Table 1 ──────────────────────────────────── Photosensitive polyvinyl alcohol Image formation Overcoat Layer material number Saponification degree Acid residue degree of polymerization Water solubility after heating ────────────────────────────────── ─── 1-A (1) 97.0% Yes 600 Yes Completely dissolved 1-b (2) 94.0% Yes 1000 Yes Completely dissolved 1-c (x) 98.5% None 600 No Insoluble ( Sludge generation) 1-d (y) 93.5% None 1000 Yes Insoluble (sludge generation) 1-e (z) 88.0% None 1000 No * Complete dissolution ───────────── ──────────────────────── Note: Image formation not possible *: No image was obtained.

As is clear from the results shown in Table 1, by using the acid-modified polyvinyl alcohol as the binder of the overcoat layer, both good image formation and water solubility of the overcoat layer after heating can be achieved. .

Example 2 The photosensitive material of Example 1 (1-
Images were formed using a) as follows. Scanning exposure at an exposure wavelength of 488 nm using an air-cooled argon ion laser as a light source (exposure on film surface: 3 μJ / cm
² ) Imagewise exposure. Next, the back surface (support side) of the photosensitive material was pressed against a hot plate heated to 145 ° C. to heat it. The surface of the photosensitive material was released under air. The heating reduces the silver halide and at the same time cures the polymerizable layer.
A silver image was visible on the exposed areas. After washing the photosensitive layer and the overcoat layer with water, using the eluent used in Example 1, brush development was carried out with an automatic etching machine, followed by thorough washing with water to elute and remove the unexposed portion of the polymerizable layer. To form a cured image. When the obtained relief image was used as a printing plate and mounted on a printing machine and printed, a good printed matter was obtained.

Example 3 Preparation of Photosensitive Material As in Example 1, an undercoat layer and a polymerizable layer were coated on an aluminum support.

"Formation of photosensitive layer" The following coating solution was prepared, coated on the polymerizable layer and dried to give a dry film thickness of about 4.0.
A μm photosensitive layer was provided.

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Acid-modified polyvinyl alcohol (12) 5.23 g of the surfactant used in Example 1. 5 wt% aqueous solution 1.68 g 10 wt% aqueous dispersion of reducing agent used in Example 1 10.08 g 0.11% aqueous solution of mercapto silver compound used in Example 1 3.20 g Halogen used in Example 1 Silver halide emulsion (4.3-fold diluted with water) 18.48 g Base precursor dispersion used in Example 1 6.00 g ────────────────────── ───────────────

(Image formation) Image exposure was performed by scanning exposure (exposure amount on film surface: 3 μJ / cm ² ) at an exposure wavelength of 488 nm using an air-cooled argon ion laser as a light source. Next, the back surface (support side) of the photosensitive material was pressed against a hot plate heated to 145 ° C. to heat it. The surface of the photosensitive material was released under air. The heating reduces the silver halide and at the same time cures the polymerizable layer. A silver image was visible on the exposed areas. When the photosensitive layer was washed and removed, the photosensitive layer was well dissolved in water. Next, using the eluent used in Example 1, brush development was carried out with an automatic etching machine, followed by thorough washing with water to elute and remove the unexposed portion of the polymerizable layer to form a cured image. Using the obtained relief image as a printing plate,
When printed on a printing machine, good printed matter was obtained.

[Example 4] "Purification of acid-modified polyvinyl alcohol (12)" The acid-modified polyvinyl alcohol (12) used in Example 3 was acetic acid produced when a vinyl acetate component was saponified into a vinyl alcohol component. It contained 5% of sodium as an impurity. 100 g of this acid-modified polyvinyl alcohol was added to 200 g of 1% hydrous methanol, and heated at 50 ° C. for 2 hours with stirring to dissolve. Then, filtration was performed to separate polyvinyl alcohol. By repeating this operation 6 times, a purified acid-modified polyvinyl alcohol (12) having a sodium acetate content of 0.3% was obtained.

[Preparation of Photosensitive Material] A photosensitive material was prepared in the same manner as in Example 3 except that the acid-modified polyvinyl alcohol (12) purified as described above was used as the binder of the photosensitive layer.

(Image formation) An image was formed in the same manner as in Example 3 using the photosensitive material prepared as described above. When the obtained relief image was used as a printing plate and mounted on a printing machine and printed, better results than those of Example 3 were obtained. That is, the number of printable sheets (the number of plates skipped, that is, the number of sheets in which highlight minute dots did not drop off on the plate) was increased by 40% or more as compared with Example 3. From this result, by reducing the sodium acetate content in the light-sensitive material,
It can be seen that the formation of a cured image is promoted and the number of printable sheets is improved.

Claims (2)

[Claims] 1. A support is provided with one or more photosensitive polymerizable layers containing a silver halide, a reducing agent and a polymerizable compound, together or separately, and further comprising a photosensitive polymerizable layer. A photosensitive material having an overcoat layer provided thereon, wherein the overcoat layer contains polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule. 2. A support, on which a polymerizable layer containing a polymerizable compound and a photosensitive layer containing silver halide are sequentially provided on a support, and a reducing agent is contained in the polymerizable layer or the photosensitive layer. A photosensitive material, wherein the photosensitive layer contains polyvinyl alcohol having an acid residue or a salt of an acid residue in the molecule.