JPH06308720A - Photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material with which high picture image density is obtd. with low fog. CONSTITUTION:This photosensitive material has one or more layers containing silver halide, reducing agent, and polymerizable compd. together or separatedly on a supporting body. The layer containing the silver halide also contains gelatine and other hydrophilic polymers. Particles of the silver halide are dispersed in the gelatine and other hydrophilic polymers. When the layer containing the silver halide is dissolved in water by 0.05g/l, pH of the obtd. soln. at 40 deg.C is <=1.2 or >=1.2 to the isoelectric point of the gelatine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-sensitive material which forms an image by polymerizing a polymerizable compound by utilizing the photosensitivity of silver halide.

[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, 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). .

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 JP-A-61-73145.
No. 4,629,676 and European Patent Publication No. 0174634A. Further, a light-sensitive material suitable for producing a printing plate using this dry image forming method is disclosed in JP-A-64-17047.
Nos. 4,985,339 and European Patent Publication No. 098522A.

In the light-sensitive material used in the image forming method 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 used in the light-sensitive material. It is an essential component. In addition,
In the present specification, the 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. Regarding a photosensitive material comprising a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound, JP-A-3-207650 (US Pat. No. 512) is used.
2443 and European Patent Publication No. 0426192A) and JP-A-4-191856.

JP-A-3-207650 and 4-1.
No. 91856 discloses gelatin and other hydrophilic polymers as binders for layers containing silver halide. In the light-sensitive material described in each publication, silver halide grains are directly dispersed in a hydrophilic polymer. In each of the above publications, a hydrophilic polymer having a low oxygen permeability (for example, polyvinyl alcohol having a high saponification degree) is preferably used as the binder. The hydrophilic polymer having a low oxygen permeability has a function of eliminating the influence of oxygen in the air on the polymerization reaction (oxygen has a polymerization inhibiting action).

[0006]

The present inventor has conducted research on a binder for a layer containing silver halide and found that a clear image can be obtained by using gelatin in combination with other hydrophilic polymers. There was found. This effect is different from the above-mentioned function of eliminating the influence of oxygen, and is effective even if a hydrophilic polymer having a low oxygen transmission rate (for example, polyvinyl alcohol having a low saponification degree) is used.

In the usual preparation of silver halide emulsions, gelatin is used as a protective colloid for silver halide grains. Gelatin has a particularly excellent function as a protective colloid. Although a method of using other hydrophilic polymer as a protective colloid instead of gelatin has been proposed, the practical protective colloid for silver halide emulsions is practically limited to gelatin. However, according to the research conducted by the present inventors, there is a problem in the function of gelatin as a binder. In an image forming system using a silver halide, a reducing agent and a polymerizable compound, if gelatin alone is used as it is as a binder for a layer containing silver halide, a clear image cannot be formed. This problem can be solved by using gelatin in combination with other hydrophilic polymers. That is, gelatin functions as a protective colloid and another hydrophilic polymer functions as a binder.

However, as a result of research conducted by the present inventor, it was found that the combined use of gelatin and other hydrophilic polymers causes another problem. When a plurality of hydrophilic polymers are used together in the same layer, phase separation easily occurs. When phase separation occurs, silver halide grains aggregate.
Aggregation of silver halide grains significantly reduces the maximum density of the image.

An object of the present invention is to provide a light-sensitive material capable of obtaining high image density with low fog.

[0010]

The above object was achieved by the light-sensitive material described in (1) below. The “layer containing silver halide” in the present specification means that the photosensitive material is a single photosensitive photosensitive layer (a silver halide, a reducing agent and a polymerizable compound are both contained in a single layer). ) Is present, it means the photosensitive polymerizable layer, and the photosensitive material is a multilayer photosensitive polymerizable layer comprising a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound. When present, it means the photosensitive layer.

(1) A light-sensitive material in which one or more layers containing silver halide, a reducing agent and a polymerizable compound are provided together or separately on a support, and the layer contains silver halide. Further contains gelatin and another hydrophilic polymer, silver halide particles are dispersed in gelatin and another hydrophilic polymer, and a layer containing silver halide is dissolved in water at a rate of 0.05 g / liter. 40 ℃ of melted liquid
2. The photosensitive material is characterized in that the pH at is 1.2 or less or 1.2 or more with respect to the isoelectric point of gelatin.

The present invention is preferably carried out in the following mode (2). (2) The light-sensitive material according to (1), wherein the gelatin is an acylated gelatin having an isoelectric point of 1.5 to 3.5.

[0013]

[Effect of the Invention] When the present inventor conducted further research,
It has been found that when the pH of the layer containing silver halide is set to the above value with respect to the isoelectric point of gelatin, the affinity between gelatin and other hydrophilic polymers is significantly improved. Thereby, phase separation and accompanying aggregation of silver halide grains can be prevented. Surprisingly, the same effect can be obtained even if the pH is 1.2 or less (acidic side) or 1.2 or more (alkaline side) with respect to the isoelectric point.

The pH value of the layer containing silver halide is
It has been conventionally adjusted in consideration of the storability of the light-sensitive material.
For example, a light-sensitive material in which the pH value of the light-sensitive layer is 7 or less is disclosed in JP-A-62-275235 (US Pat. No. 4,853,331).
2 and European Patent Publication No. 0247396A). However, the disclosure of this publication relates to a light-sensitive material containing silver halide grains in microcapsules. There is no disclosure of an embodiment in which silver halide grains are directly dispersed in a hydrophilic polymer such as gelatin. The pH value is set independently of the isoelectric point of gelatin.

The present invention solves the problem in the case where gelatin and another hydrophilic polymer are used in combination and the silver halide grains are dispersed therein, unlike the above-mentioned prior art. In the light-sensitive material of the present invention, aggregation of silver halide grains is prevented, and a clear image having low fog and high image density can be formed.

[0016]

DETAILED DESCRIPTION OF THE INVENTION In the light-sensitive material of the present invention, a solution of a layer containing silver halide dissolved in water at a rate of 0.05 g / liter has a pH at 40 ° C. of 1 relative to the isoelectric point of gelatin. .2 or less or 1.2 or more. In other words, the difference between the pH value of the layer containing silver halide and the isoelectric point of gelatin is 1.2 or more. This pH is substantially the same as the pH of the coating liquid when a layer containing silver halide is formed by coating in the process of manufacturing a light-sensitive material. Incidentally, the above-mentioned pH at 40 ° C. is a value 1.2 or more than the isoelectric point,
That is, it is preferably on the alkaline side. Also, p
H is 1.4 or lower than the isoelectric point of gelatin or 1.4
It is also preferable that the value is the above or more. The difference between the pH and the isoelectric point of gelatin may be even larger. However, in reality, the difference is about 5.0, and even if the difference is made larger than this, the effect is not particularly improved.

Various methods can be used to adjust the pH of the layer containing the silver halide. However, the method of setting the pH of the coating solution for the layer containing silver halide is the easiest and preferable in the preparation stage of the light-sensitive material. Specifically, an acid or alkali may be added to the coating solution for the layer containing silver halide. The acid used for pH adjustment may be either an organic acid or an inorganic acid. Further, as the alkali, an organic or inorganic basic substance can be used. It is preferable to suppress the fluctuation of pH due to an additive in the preparation of a coating solution for a layer containing silver halide, reduce the influence of dissolved carbon dioxide gas during storage of the coating solution, and stabilize the pH value of the solution. For this purpose, various pH buffers are used. For the pH buffer solution, see Kagaku Binran Basic Edition II (Maruzen Co., Ltd. 196).
There is a description in 12.3 buffer solution of 6).

In the present invention, the layer containing silver halide contains gelatin. Gelatin is classified into acid-processed gelatin, alkali-processed gelatin, and enzyme-processed gelatin by hydrolysis treatment. Both are applicable to the present invention. Generally, alkali-processed gelatin, especially lime-processed gelatin is mainly used. Gelatin is also classified according to the type of raw material. In the present invention, osseous gelatin is particularly preferably used. Gelatin derivatives can also be used in the present invention. For gelatin derivatives, acylation (eg,
Phthalated) gelatin, carbamylated (eg phenylcarbamylated) gelatin and graft copolymers of gelatin with other polymers. In the present invention, acylated gelatin, particularly phthalated gelatin is preferably used. The term "gelatin" as used herein includes these gelatin derivatives. Depending on the type of gelatin as described above,
The isoelectric points are significantly different. The isoelectric point of alkali-processed gelatin is 4.7 to 5.3. The isoelectric point of acid-treated gelatin is 7-9. In addition, acylated gelatin, especially acylated gelatin using dibasic acid such as phthalation,
The isoelectric point drops significantly to 1.5 to 3.5. The isoelectric point of gelatin is measured by isoelectric focusing (Maxey, C.
R (1976); Photogr.Gelatin 2, Editor Cox, PJ Acade
mic, London, Engl.) or ion exchange resin method. The isoelectric point values of the same sample are slightly different depending on the measuring method, but they are not so different as to affect the regulation of the pH value in the present invention. Further, the isoelectric point of gelatin has a distribution, but the pH can be defined by representing it with an average value.

Gelatin functions as a protective colloid for silver halide grains. Therefore, it is preferable to use gelatin in the preparation of silver halide emulsion. The amount of gelatin used is preferably in the range of 0.05 to 2.0 in weight ratio with respect to the value obtained by converting the amount of silver contained from the used silver halide, and 0.1 to 1. 0
The range of 0.15 to 0.
Most preferably, the range is 7.

In the present invention, the layer containing silver halide further contains a hydrophilic polymer other than gelatin. The hydrophilic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in the molecular structure. Examples of hydrophilic groups include carboxyl, alcoholic hydroxyl group, phenolic hydroxyl group,
Mention may be made of sulfo, sulfonamide groups, sulfonimides and amides. Examples of hydrophilic bonds include urethane bonds, ether bonds and amide bonds. It is preferable to use a water-soluble polymer or a water-swellable polymer as the hydrophilic polymer. The water-swellable polymer is a polymer which has an affinity for water but is not completely dissolved in water due to a cross-linked structure of the polymer. As the water-soluble or water-swellable polymer, a natural or synthetic polymer compound can be used. Water-soluble polysaccharides can be used as the natural polymer. Examples of water-soluble polysaccharides can include starch, starch derivatives, cellulose, cellulose derivatives, alginic acid, pectic acid, acacia, pullulan and dextran. If necessary, these natural polymers may be artificially modified before use. Further, in the preparation of a light-sensitive material, a natural polymer can be modified or cross-linked before use. As the synthetic polymer, a polymer of a monomer having a hydrophilic group or a hydrophilic bond as described above or a copolymer of the monomer and another monomer can be used. In the present invention, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide and derivatives or modified products thereof can be preferably used. Polyvinyl alcohol is particularly preferred.

Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen transmission rate, the saponification degree is preferably 50% or more, more preferably 80% or more, and 9
It is particularly preferable to be 5% or more. Copolymer modified polyvinyl alcohol can also be used. Copolymerization modification is a method of synthesizing modified polyvinyl alcohol by saponifying a copolymer of vinyl acetate and another monomer. As the monomer to be copolymerized, any monomer can be used as long as it is copolymerized with vinyl acetate. Examples of such monomers include:
Mention may be made of ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, methyl methacrylate and acrylamide. Further, post-modified polyvinyl alcohol can also be used. With post-modification, by using a compound having reactivity with the hydroxyl group of polyvinyl alcohol,
This is a method of denaturing by a polymer reaction after synthesis of polyvinyl alcohol. Specifically, the hydroxyl group of polyvinyl alcohol is modified by etherification, esterification or acetalization. Furthermore, it is also possible to use crosslinked polyvinyl alcohol. As a cross-linking agent,
Aldehydes, methylol compounds, epoxy compounds, diisocyanates, divinyl compounds, dicarboxylic acids or inorganic crosslinking agents (eg boric acid, titanium, copper) can be used.

A hydrophilic polymer other than gelatin functions as a binder for the layer containing silver halide. Therefore, it is preferable to add a hydrophilic polymer to a prepared silver halide emulsion to prepare a coating solution for a layer containing silver halide. The molecular weight of the hydrophilic polymer is 3000 to 50
The range of ten thousand is preferable. The amount of hydrophilic polymer used is 0.0
It is preferably 5 to 20 g / m ² , and more preferably 0.1 to 10 g / m ² . The hydrophilic polymer is used in a weight ratio of 5 to gelatin.
Preferably in the range of 10 to 500
The range of 0 is more preferable.

The present invention is particularly effective in a light-sensitive material containing a compound having a mercapto group in a light-sensitive polymerizable layer. In the conventional image forming method, a compound having a mercapto group is often added to the photosensitive polymerizable layer in order to obtain an image with high density. The compound having a mercapto group is an aliphatic, aromatic or heterocyclic compound having 1 or 2 mercapto groups as a substituent. The hydrogen atom of the mercapto group (-SH) may be replaced by a silver atom or an alkali metal atom. Regarding the compound having a mercapto group, JP-A-63-301036
Nos. 63-301037 and 64-2035. When a compound having a mercapto group is used, the agglomeration of silver halide described above is likely to occur. When the pH of the layer containing silver halide is adjusted according to the present invention, remarkable aggregation of silver halide when a compound having a mercapto group is used can be prevented.

[Layer Structure of Photosensitive Material] The layer structure of the photosensitive material of the present invention 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, the photosensitive material may have a constitution of three or more layers consisting of a photosensitive layer, a polymerizable layer and other functional layers. Other functional layers include
An image formation promoting layer, an adhesive layer and a release layer are included.

[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 0.3 to 7 μm.

[Overcoat layer or image formation accelerating layer] The overcoat layer has a function of protecting the light-sensitive material and preventing oxygen from entering the air to enhance the degree of curing of the polymerizable layer. The image formation promoting layer is a layer in which the overcoat layer contains a component that promotes image formation (eg, a base or a base precursor, a reducing agent, a thermal development accelerator), and has a function of promoting image formation. At the same time, it also has a protective function as the above-mentioned overcoat layer. These layers can contain 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 0.3 to 20.
The thickness is preferably μm, more preferably 0.5 to 10 μm. The overcoat layer and the image formation promoting layer are generally formed using a hydrophilic polymer.
However, it is also possible to use a hydrophobic polymer. For example, it can be formed by dissolving a hydrophobic polymer in a solvent and coating it. It can also be formed by coating a polymer latex. If a hydrophobic polymer is used for the etching treatment, these layers must be removed by peeling after thermal development and prior to etching.

[Adhesive Layer] When an image is formed using 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.

[Peeling Layer] When an image is formed by transfer, a peeling 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, preferable support materials are aluminum plate, polyethylene terephthalate film, 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 the 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 in which a current is applied to an aluminum plate in a hydrochloric acid or nitric acid electrolytic solution to grain the grain) 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 sanding the aluminum surface with a polishing ball and an abrasive, and a brush grain method of sanding the surface with a nylon brush and an abrasive. Law).

Next, the aluminum plate subjected to the graining treatment 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 alkaline etching, the aluminum plate is washed with 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 constituent of 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,
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 the silver halide, any of silver chloride, silver bromide, silver iodide, 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 are no particular restrictions 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 include copper, thallium, lead, bismuth, cadmium, zinc, chalcogen (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 via a redox reaction with an oxidizing agent of a first reducing agent produced by reduction of silver halide (and / or organic silver salt) with another reducing agent coexisting with the reducing agent. (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 type and amount of the reducing agent, the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed 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 the function of suppressing polymerization, it is necessary to include a polymerization initiator (radical generator) together with the reducing agent. A portion where a latent image of silver halide is not formed (when the oxidation inhibitor has a stronger polymerization inhibiting function than the reducing agent) or a 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 of Polymer Science and Technology, Editorial Committee for Polymer Studies 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 the binder include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), polycondensation type synthetic homopolymers and copolymers (eg, polyester, polyamide, polyurethane, 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 contains only the polymerizable monomer without containing the binder, 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.

[Hydrophilic Polymer] The hydrophilic polymer used in the photosensitive layer (layer containing silver halide) has been described above. These hydrophilic polymers are also used as a binder for hydrophilic layers such as overcoat layers and image formation promoting layers.

[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). Further, 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 poorly 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 pigment and color index (CI) handbook, "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 methods include 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. The above-mentioned surface treatment methods are "property and application of metallic soap" (Koshobo), "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, an additive such as an antifoggant, a silver development accelerator that promotes silver development, and a stabilizer is 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 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 after proper development to lower the concentration of the base in the layer to stop the development or interact with silver and a silver salt to suppress development. 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 or the image formation accelerating layer provided on the uppermost layer on the side coated with the light-sensitive layer is a common silver salt photograph. Is a discontinuous solid particle of an inorganic or organic material dispersible in a hydrophilic colloid binder well known in the technical field and. 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,
Mention may be made of magnesium sulphate, potassium carbonate), non-image forming silver halide grains and glass.
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 alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates,
Alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide,
Included are homopolymers or copolymers of methacrylamide, vinyl esters, acrylonitrile, olefins, styrene or benzoguanamine. In the case of the above copolymer, examples of other copolymerized units include acrylic acid,
Methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, sulfoalkyl acrylates, sulfoalkyl methacrylates and styrene sulfonic acids can be mentioned. In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinylcarbazole,
Polyvinylidene chloride can also be used. Further, an alkali-soluble matting agent such as an alkyl methacrylate / methacrylic acid copolymer (JP-A-53-7231 and JP-A-58-66).
937 and 60-8894) and an alkali-soluble polymer having an anionic group (JP-A-58).
No. 166341). The particle size of the matting agent is preferably in the range of 1 to 50 μm. The particle size distribution is
It may be monodisperse or polydisperse. A matting agent whose maximum particle size does not exceed 30 μm.
It is particularly preferable that the content of m or more is 10 vol.% or less. The amount of the above matting agent used is 0.01 to 1 g / m ^2.
Is preferably used in the range of 0.1 to 0.7 g /
More preferably, it is used in the range of 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, arylphosphite, p
-Toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol, pyrogallol, hydroquinone, and alkyl- or aryl-substituted hydroquinone.

Next, each step of image formation will be described. [Image exposure] 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 lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, and various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, (Helim cadmium laser), a light emitting diode, a cathode ray tube and the like. 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 dose is determined by the sensitivity of silver halide,
Generally, it is in the range of 0.01 to 10000 ergs / cm ² , more preferably 0.1 to 1000 ergs / cm ² . When the support is transparent, it is also possible to expose through the support from the back side of the support.

[Development Processing] The development of the light-sensitive material is generally carried out by a dry method (heat development) by heating. However, a wet development process using a developing solution may be adopted. The heat development can be performed by a method of bringing the heat-sensitive material into close contact with a heated object (for example, a metal plate, a block, a roller), a method of immersing it in a heated liquid, a method of irradiating infrared rays, or the like. The surface of the light-sensitive material may be opened to the air and heated from the side of the support, or the surface may be brought into close contact with a heating object and heated with the air blocked. When the surface is exposed to the air and heated, oxygen in the air may permeate into the light-sensitive material to inhibit the polymerization reaction, so that at least a part of the layer of the light-sensitive material has the above-mentioned oxygen permeability. It is preferred to use low polymers as binders. The heating temperature is 60 to 200 ° C., more preferably 100 to 150
It is in the range of ° C. The heating time is in the range of 1 to 180 seconds, more preferably 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 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 a thermal polymerization initiator is used, heating can be performed only once, because radicals can be generated by heating during thermal development. When a photopolymerization initiator is used, it is necessary to expose the entire surface after thermal development in order to generate radicals. 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 is 1
It is in the range of 0 ^{3 to} 10 ⁷ ergs / cm ² .

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

[Elution (Etching) Process] In the elution process, the difference in solubility between the uncured portion and the cured portion is used to elute only the uncured portion to form a polymer image. Generally, after thermal development, the photosensitive material is immersed in a liquid (etching solution) capable of removing the uncured portion of the polymerizable layer. For the etching solution,
A liquid that dissolves or swells the uncured polymerizable layer, such as an organic solvent, an alkaline aqueous solution or a mixture 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. As the organic solvent, a lower alcohol (eg, methanol, ethanol, propanol,
Butanol), aromatic ring-containing alcohol (eg, benzyl alcohol, phenethyl alcohol), ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and the amino alcohols described above as the base. Further, a surfactant, a defoaming agent, and other additives can be added to the etching solution, if necessary. Further, 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 immersed in the etching solution, or the photosensitive layer other than the polymerizable layer may be previously washed with water, or may be peeled and removed to be immersed in the etching solution. .

[Removal Treatment (by Sheet)] By utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion, the uncured portion or the cured portion is selectively separated into another sheet (removal sheet).
And remove it. As a result, the portion remaining on the photosensitive material is used as an image. The removal sheet may be laminated with the photosensitive material before image exposure or development.

[Transfer Treatment] The uncured portion or the cured portion is selectively adhered to another sheet (image receiving material) by utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion. To transfer. 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.

[Toner Development Processing] A coloring substance (toner) is selectively adhered to the uncured portion or the cured portion to visualize the image. Toner can be attached to the uncured portion by utilizing the difference in surface tackiness between the uncured portion and the cured portion. Further, after selectively removing the uncured portion or the cured portion, the toner may be attached to the remaining portion. 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 selectively transferred to the uncured portion or the cured portion.

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" After graining the surface of an aluminum plate having a thickness of 0.30 mm with a nylon brush and a water suspension of pumicetone (400 mesh), water was applied. Washed well with. Next, it was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, and then washed with running water. Neutralize with 20% aqueous nitric acid, wash,
I washed it with water. The obtained aluminum plate was subjected to a sinusoidal alternating wave current (conditions: voltage at anode 12.7 v, ratio of electricity at cathode to electricity at anode was 0.8, electricity at anode was 16
Electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution using 0 Coulomb / dm ² ). The surface roughness of the obtained plate was 0.
It was 6 μm (Ra indication). Following this process, 30
% Desulfuric acid aqueous solution at 55 ° C. for 2 minutes. Next, anodization treatment was performed in a 20% sulfuric acid aqueous solution so that the thickness was 2.7 g / dm ² (current density: 2 A / d
m ² ). The obtained aluminum plate was immersed in a 3 wt% sodium silicate aqueous solution at 70 ° C. for 20 minutes and washed with water,
Dried.

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

──────────────────────────────────── Coating solution for the polymerizable layer ───── ─────────────────────────────── Dipentaerythritol hexaacrylate 2.5g Allyl methacrylate / methacrylic acid copolymer (copolymerization Ratio = 83/17) 20% by weight propylene glycol monomethyl ether solution 37.5 g Pigment dispersion below 13.0 g Fluorine-based nonionic surfactant (MEGAFAC F-172 manufactured by Dainippon Ink and Chemicals, Inc.) 01 g Methyl ethyl ketone 37.0 g Propylene glycol monomethyl ether 37.0 g ─────────────────────────────────────

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Chromophtal red A2B 18g Benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 12 g Cyclohexanone 30 g Propylene glycol monomethyl ether 40 g ─────────────────────────────────────

"Formation of photosensitive layer" (Preparation of silver halide emulsion) a. Preparation of Emulsion (Em-1) A container containing lime-treated ossein gelatin (isoelectric point: 5.0), potassium bromide and water and heated to 55 ° C., the following thioether compound was added to the total amount of silver nitrate. 2.0 × 1
After addition in an amount corresponding to 0 ^-3 mol, while maintaining the pAg in the reaction vessel at 9.2, the aqueous solution of silver nitrate and the molar ratio of rhodium to the total amount of potassium iodide and silver nitrate were 4 × 1.
An aqueous potassium bromide solution containing rhodium ammonium chloride was added so as to be 0 ^-8 mol by the pAg controlled double jet method to form silver iodobromide grains. Then, at 55 ° C., a solution of the following spectral sensitizing dye in methanol (10 ⁻² M / L) was added to this emulsion at 1 mg of silver nitrate.
200 ml was added to a mole equivalent emulsion. Further, subsequently, at the same temperature and pAg = 8.9, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridium (III) salt was added so that the molar ratio of iridium to silver was 10 ^-7 mol were controlled. The second stage addition was carried out by the double jet method to prepare core / shell type silver iodobromide emulsion grains having the following composition. The isoelectric point of the lime-treated ossein gelatin is a value measured according to the sucrose concentration gradient isoelectric focusing method (Toda, Y. (1988), 5th IAG Conference).

Core: silver iodobromide (silver iodide content: 3.5 mol%) Shell: pure silver bromide Core / shell ratio: 5/5 (silver mol ratio) Average silver iodide content: 1. 8 mol% average particle size: 0.35 μm

These emulsion grains were monodisperse and 98% of all grains were present within ± 40% of the average grain size.
Next, this emulsion was washed with water and desalted, and then pH was adjusted to 6.2 and pA.
After adjusting g to 8.9, gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid to prepare a silver halide emulsion (Em-1).

[0080]

[Chemical 1]

[0081]

[Chemical 2]

B. Preparation of emulsion (Em-2) 95% phthalated ossein gelatin (isoelectric point:
2.5), potassium bromide and water are added to a container heated to 55 ° C., and the above thioether compound is added in an amount corresponding to 2.0 × 10 ⁻³ mol based on the total amount of silver nitrate added. While maintaining pAg in the reaction vessel at 9.2, an aqueous solution of silver nitrate,
An aqueous potassium bromide solution containing rhodium ammonium chloride so that the molar ratio of rhodium to the total amount of potassium iodide and silver nitrate added is 4 × 10 ⁻⁸ mol;
pAg controlled double jet method,
Silver iodobromide grains were formed. Then, at the same temperature and the same p
H, pAg = 8.9, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridium (III) was added so that the molar ratio of iridium to silver was 10 ⁻⁷ by controlled double jet method. While adding the second step, 200 ml of the above-mentioned methanol solution of the spectral sensitizing dye (10 ^-2 M / L) was continuously added at a uniform rate to an emulsion corresponding to 1 mol of silver nitrate. Core / shell type silver iodobromide emulsion grains having the above composition were prepared. In addition,
The isoelectric point of the phthalated ossein gelatin is sucrose concentration gradient isoelectric focusing method (Toda, Y. (1988), 5th
It is the value measured according to the IAG Conference.

Core: Silver iodobromide (silver iodide content: 8.5 mol%) Shell: Pure silver bromide Core / shell ratio: 3/7 (silver mol ratio) Average silver iodide content: 2. 6 mol% average particle size: 0.35 μm

These emulsion grains were monodisperse and 98% of all grains were present within ± 40% of the average grain size.
Next, this emulsion was washed with water and desalted, and then pH was adjusted to 6.2 and pA.
The g was adjusted to 8.9 to prepare a silver halide emulsion (Em-1).

(Preparation of Reducing Agent Dispersion) 10 g of a powder of the following reducing agent 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 0.5 μm or less.

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[Chemical 3]

(Formation of Photosensitive Layer) A coating solution of the following components was prepared, and a Michaelis buffer solution was selected and used according to the pH range as described below, and the pH was adjusted as shown in Table 1 below. It was adjusted. pH <5.5 Acetic acid-sodium acetate buffer (however, for pH = 2.4, phosphoric acid aqueous solution was further added) pH> 5.5 Potassium dihydrogen phosphate-disodium hydrogen phosphate buffer pAg was adjusted to 9.1 at all levels by the addition of KBr aqueous solution. The resulting liquid was applied onto the polymerizable layer and dried to form a photosensitive layer having a dry film thickness of about 1.2 μm.

──────────────────────────────────── Coating solution for the photosensitive layer ───── ─────────────────────────────── Polyvinyl alcohol with a saponification degree of 79.5% (trade name: PVA-420, 60.0 wt% aqueous solution of Re Co., Ltd. 90.0 g Dispersion of the above reducing agent 10.0 g 0.10 wt% methanol solution of the following additives 7.0 g Silver halide emulsion 3.7 g of the following surfactants 5 wt% aqueous solution 3.5 g water 70.0 g ─────────────────────────────────────

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[Chemical 4]

[0090]

[Chemical 5]

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[Table 1] Table 1 ──────────────────────────────────── Sample number Emulsion Gelatin Isoelectric point Photosensitive layer pH pH-isoelectric point ───────────────────────────────────── 1 Em-1 5. 0 2.4 -2.6 2 Em-1 5.0 4.6 -0.4 3 Em-1 5.0 6.8 +1.8 4 Em-1 5.0 7.5 +2.5 5 5 Em -2 2.5 3.1 +0.6 6 Em-2 2.5 4.7 +2.2 7 Em-2 2.5 6.1 +3.6 8 Em-2 2.5 7.3 +4.8 ────────────────────────────────────

The pH of a solution prepared by dissolving the photosensitive layer in water at 40 ° C. at a rate of 0.05 g / l was measured.
It was in good agreement with H. Separately, only the coating solution for the photosensitive layer was applied onto a transparent polyethylene terephthalate support and observed under a microscope to evaluate the degree of dispersion of silver halide grains.
The results are shown in Table 2 below.

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

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[Chemical 6]

(Formation of Image Formation Accelerating Layer) A liquid having the following composition was mixed to prepare a coating liquid. This was applied onto the photosensitive layer and dried to form an image formation promoting layer having a dry film thickness of about 3.3 μm.

──────────────────────────────────── Coating solution for the image formation promoting layer ──── ──────────────────────────────── Polyvinyl alcohol with a saponification degree of 88.0% (trade name: PVA-205, 10% by weight aqueous solution of Kuraray Co., Ltd. 100.0 g Propionamide 2.0 g The above base precursor dispersion 4.0 g 5% by weight aqueous solution of the above-mentioned surfactant 2.0 g ────────── ────────────────────────────

As described above, the light-sensitive materials (Sample Nos. 1 to 1)
8) was created. A developing film was adhered to each light-sensitive material, and scanning exposure was performed using an argon ion laser (488 nm). Next, the back surface of the exposed light-sensitive material (the surface on the side of the aluminum support on which the layer is not provided)
Was adhered to a hot plate heated at 140 ° C for 40 seconds, and a 20 μm thick polyethylene terephthalate film having a surface matted by applying silica particles having an average particle size of 10 μm was adhered to the image formation promoting layer surface. Thermal development was performed in the as-prepared state. The heat-developed photosensitive material is immersed in an etching solution (Fuji PS Developer DN-3C, manufactured by Fuji Photo Film Co., Ltd.) at room temperature for 1 minute to be etched, and then rinsed well to elute the photosensitive layer in the unexposed area. Remove it
A relief image of the polymer was formed on the exposed areas.

(Measurement of Image Density) The reflection density of the obtained image was measured through a green filter using an X-rite-301 type reflection densitometer, and the maximum density (D _max ) of the image was obtained.
And the minimum density (D _min ) was determined. The maximum concentration and the minimum concentration were determined by subtracting the concentration by the support from the measured maximum concentration and minimum concentration, respectively. The results are shown in Table 2.

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[Table 2] Table 2 ──────────────────────────────────── Sample number pH-isoelectric point Dispersion of particles Maximum concentration Minimum concentration ──────────────────────────────────── 1-2.6 Very slight Aggregated to 1.47 0.02 2 −0.4 Most are aggregated 0.15 0.03 3 +1.8 Good 1.58 0.02 4 +2.5 Good 1.61 0.03 5 +0.6 Large Part is agglomerated 0.21 0.06 6 +2.2 Very slightly agglomerated 1.43 0.02 7 +3.6 Good 1.54 0.02 8 +4.8 Good 1.60 0.03 ───── ───────────────────────────────

As is clear from the results shown in Table 2, when the difference in isoelectric point between the layer containing silver halide and gelatin is large, the light-sensitive material exhibits excellent photographic characteristics, high image density and low fog level. It is possible to form a clear image. The relief images obtained by the above sample numbers 1, 3, 4, and 6 to 8 were used as printing plates, and a printing machine (Heidel KOR-
When it was mounted on D) and printed, good printed matter was obtained.

Claims (2)

[Claims] 1. A photosensitive material provided with one or more layers containing a silver halide, a reducing agent and a polymerizable compound together or separately on a support, wherein the layer containing silver halide comprises Further contains gelatin and other hydrophilic polymers,
The silver halide grains are dispersed in gelatin and other hydrophilic polymers, and the silver halide containing layer has a grain size of 0.
A photosensitive material characterized in that the pH of a solution dissolved in water at a rate of 05 g / liter at 40 ° C. is 1.2 or less or 1.2 or more with respect to the isoelectric point of gelatin. 2. The light-sensitive material according to claim 1, wherein the gelatin is an acylated gelatin having an isoelectric point of 1.5 to 3.5.