JPH07230170A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material capable of forming a hardened image small in fog and large in exposure latitude in heat development conditions by adding a nonpolymerizable oily substance in any layer. CONSTITUTION:The photosensitive material has >=2 layers containing silver halide, a reducing agent, and a cross-linkable polymer on a support, and a photosensitive layer containing silver halide and a hardenable layer containing the cross-linkable polymer are separately formed, and the oily substance is added to one of the layers, preferably, to any layer except the layer farthest from the support, especially, to the hardenable layer or its adjacent layer, preferably, its adjacent photosensitive layer. The water solubility of the hydrophobic substance at a room temperature of 25 deg.C is <=10%, and when organic compounds are used for the oily substance, greater parts of the bonds between the carbon atoms of the compounds must be saturated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive material which forms a cured image of a crosslinkable polymer 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 Laid-Open Nos. 61-69062 and 61-73145 (US Pat.
676 and European Patent Publication No. 0174634A). In this method, an oxidant radical of a reducing agent obtained by reducing silver halide (a radical generated by decomposition of an oxidant of the reducing agent may be used.
Hereinafter, this is simply referred to as an oxidant radical. ) Initiates the polymerization.

Photosensitive materials suitable for the production of printing plates using this image forming method are disclosed in JP-A-5-249667 (specifications of US Pat. No. 5,124,443 and European Patent Publication No. 0426192A) and JP-A-4. -19
No. 1856. Furthermore, an image forming method suitable for creating a color proof is disclosed in Japanese Patent Laid-Open No. 4-338.
No. 955, No. 4-338956, No. 4-340548.
And No. 5-6003. In the production of printing plates or color proofs described in the above publications, it is described that a crosslinkable polymer is used in addition to or instead of the polymerizable compound. Further, in a light-sensitive material used for such image formation, a light-sensitive layer containing silver halide and a curable layer containing a crosslinkable polymer are often provided separately. The use of crosslinkable polymers to form the image enhances the cured image. Also, the image can be enhanced by separating the photosensitive layer and the curable layer. Further, the strength of the image is required for the application of the printing plate or the color proof. Therefore, in the production of a printing plate or a color proof, it is preferable to provide a curable layer containing a crosslinkable polymer separately from the photosensitive layer.

[0004]

DISCLOSURE OF THE INVENTION The present inventor has conducted research on a photosensitive material provided with a curable layer containing a crosslinkable polymer. As a result, in the light-sensitive material provided with such a curable layer, a phenomenon in which fog increased in a cured image was observed with an increase in heat development temperature or extension of heat development time. Further, the tone reproducibility of the halftone image may be rapidly deteriorated. In particular, the shadow portion of the cured image is easily crushed.
Therefore, in a light-sensitive material provided with a curable layer of a crosslinkable polymer, the heat development temperature and the heat development time must be strictly controlled. That is, such a photosensitive material has a narrow latitude with respect to thermal development conditions.

An object of the present invention is to provide a light-sensitive material capable of forming a cured image with less fog and having a wide latitude with respect to thermal development conditions.

[0006]

The above objects have been achieved by the following photosensitive material (1). (1) Two or more layers containing silver halide, a reducing agent and a crosslinkable polymer are provided on a support, and a photosensitive layer containing silver halide and a curable layer containing a crosslinkable polymer are separately provided. The light-sensitive material provided in 1., wherein any of the layers contains a non-polymerizable oily substance.

The above light-sensitive material can be implemented in the following modes (2) to (10). (2) The photosensitive material according to (1), wherein the curable layer further contains a polymerizable compound. (3) The photosensitive material according to (1), wherein the oily substance is contained in any layer other than the layer farthest from the support. (4) The photosensitive material according to (1), wherein the oily substance is contained in a curable layer or a layer adjacent to the curable layer. (5) The photosensitive material according to (1), wherein the oily substance is contained in a curable layer or a photosensitive layer. (6) The solubility of the above oily substance in water at room temperature is 10%.
The photosensitive material as described in (1) below. (7) The photosensitive material according to (1), wherein the oily substance is a liquid at room temperature. (8) The above-mentioned oily substance has 9 carbon-carbon bonds in the compound.
The photosensitive material according to (1), which is an organic compound in which 0% or more is saturated. (9) The photosensitive material according to (1), wherein the oily substance is a polar compound having a relative dielectric constant of 3.0 or more. (10) The oily substance is 1 to 1 with respect to the crosslinkable polymer.
The photosensitive material according to (1), which is contained in an amount of 50% by weight.

[0008]

According to the research conducted by the present inventors, when a non-polymerizable oily substance is added to any layer of a light-sensitive material, the above-mentioned problems relating to the light-sensitive material provided with a curable layer containing a crosslinkable polymer are solved. can do. In a photosensitive material provided with a curable layer containing a crosslinkable polymer, an oily substance is presumed to act as in the following (A) to (C). The non-polymerizable oily substance (A) suppresses an excessive curing reaction of the crosslinkable polymer, and prevents an increase in fog and a thick image. (B) During heat development, the curable layer is selectively (chemically) cured in exposed or unexposed areas. However, when the curable layer is heated, the portion that should not be cured becomes physically hard due to the entanglement of the polymer, crystallization, or evaporation of the residual solvent. The physically hardened part has reduced solubility in the eluate and increased fog. The non-polymerizable oily substance suppresses this physical hardening. The non-polymerizable oily substance (C) also has a function of directly promoting the dissolution of the crosslinkable polymer in the eluate. As a result, the photosensitive material of the present invention solves the problem of the curable layer containing a crosslinkable polymer and has a wide latitude with respect to the heat development conditions.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The light-sensitive material of the present invention is characterized in that a non-polymerizable oily substance is added to any layer.
The non-curable oily substance is preferably added to any layer other than the layer farthest from the support, and more preferably to the curable layer or its adjacent layer. The adjacent layer is preferably added to the photosensitive layer. The solubility of the hydrophobic substance in water at room temperature (25 ° C) is 10% or less. It is preferably 3% or less, more preferably 1% or less.

The oily substance is preferably a liquid at room temperature. Specifically, the melting point is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and most preferably 10 ° C. or lower. On the other hand, the boiling point is preferably 150 ° C. or higher. In order to be a liquid at room temperature, the molecular weight is preferably 3000 or less. Since the oily substance is used to prevent the curable layer from being excessively cured, a compound having polymerizability (curability) or tackiness is not preferable. Therefore, when an organic compound is used as the oily substance, most (90% or more) of carbon-carbon bonds in the compound are saturated (preferably all saturated), or an unsaturated organic compound. Even in this case, it is preferable to use an organic compound that is aromatic rather than aliphatic. The oily substance may have some hydrophilic atomic groups as long as it is hydrophobic as a whole.

Preferred oily substances are esters,
Higher alcohols and oils are available. Examples of esters include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, triphenyl phosphate, dibutyl sebacate, butyl oleate and butyl stearate. Examples of higher alcohols include stearyl alcohol and oleyl alcohol. Examples of fats and oils are linseed oil,
Includes olive oil, tung oil, sesame oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, castor oil, cottonseed oil and coconut oil. As the oily substance, a highly polar compound is preferable. Specifically, it is preferable to use a compound having a relative dielectric constant of 3.0 or more. For example, tricresyl phosphate having a relative permittivity of 6.9 and dibutyl phthalate having a relative permittivity of 6.4 are preferably used.

When the solvent of the coating liquid for the layer to which the oily substance is added is an organic solvent, the oily substance can be directly dissolved in the coating liquid. When the solvent of the coating liquid is water, an oily substance emulsified and dispersed in water (or an aqueous solution of a water-soluble polymer) can be added to the coating liquid. When the oily substance is emulsified, it is generally contained in the layer in the form of droplets. The average size of the oily substance droplets or particles is 0.1 to 10 μm.
Is preferable, and 0.3 to 3 μm is more preferable. The preferable amount of the oily substance used differs depending on whether the oily substance is added to the curable layer or the hydrophilic layer such as the photosensitive layer. When added to the curable layer, it is preferably in the range of 1 to 50% by weight of the crosslinkable polymer,
More preferably, it is in the range of 3 to 30% by weight. When added to a hydrophilic layer such as a photosensitive layer, the upper limit is 30
It is preferably not more than 10% by weight, more preferably not more than 10% by weight, most preferably not more than 5% by weight. The lower limit of the amount added to the hydrophilic layer is the same as the amount added to the curable layer.

[Layer Constitution of Light-Sensitive Material] In the light-sensitive material of the present invention, at least two kinds of layers, that is, a light-sensitive layer containing silver halide and a curable layer containing a crosslinkable polymer are provided on a support. The photosensitive material may have a constitution of three or more layers comprising a curable layer, a photosensitive layer and an overcoat layer or an image formation promoting layer. Further, the photosensitive material may be provided with another functional layer. Other functional layers include adhesive layers and release layers.

[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, 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. Aluminum plates are particularly preferred.

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 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 an aqueous sodium silicate 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 curable layer and the printing characteristics.

[Undercoat layer] As components constituting the undercoat layer, polymers (eg, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid); amines (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.

[Photosensitive Layer] The photosensitive layer contains silver halide and generates radicals by imagewise exposure and thermal development. The generated radicals diffuse and enter the curable layer to cure the curable 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.

[Curable Layer] The curable layer contains a crosslinkable polymer. In addition to the crosslinkable polymer, a polymerizable compound may be added to the curable layer. In order to obtain an image with a high degree of curing (strength), it is preferable to add a polymerizable compound to the curable layer. The curable layer is cured by polymerization or crosslinking of the crosslinkable polymer. The thickness of the curable layer is 0.1 to 20 μ
The thickness is preferably m, and more preferably 0.3 to 7 μm. The crosslinkable polymer (and polymerizable compound) is preferably uniformly contained in the curable layer without using microcapsules.

[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 curable 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 overcoat layer and the image formation promoting layer are generally formed using a hydrophilic polymer. The thickness of these layers is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm.

[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.

[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.

[Silver Halide] As the silver halide,
Grains of silver chloride, silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. 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. Anomalous crystal forms include potato, spherical, plate and plate 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 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] In the photosensitive layer of the photosensitive material,
Organometallic salts can be added with the 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,
Examples thereof include thiadiazoles, azaindenes, and aliphatic, aromatic or heterocyclic compounds having a mercapto group as a substituent. 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, and preferably 10 ⁻⁵ mol, per mol of silver halide.
^{-4 to} 1 mol is used. Also, instead of the organic silver salt,
You may add the organic compound which comprises it to a photosensitive layer, and it may react with a silver halide in a photosensitive layer, and may convert it into an organic silver salt.

[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 having a basicity to form a salt with an acid can also be used in the form of a salt with an appropriate acid. These reducing agents may be used alone, or as described in each of the above publications, two or more reducing agents may be used in combination. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. Cause the polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant 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 type and amount of the reducing agent, the polymerizable compound in the portion of the silver halide latent image formed portion or the latent image not formed portion 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] The thermal polymerization initiator is a compound capable of decomposing upon heating to generate free radicals which can be added to the polymerizable compound or the crosslinkable polymer. Regarding the thermal polymerization initiator, "Addition Polymerization / Ring-Opening Polymerization" edited by The Society of Polymer Science and the Society for Polymer Experiments Editorial Committee (1983,
Kyoritsu Shuppan), pages 6-18 and JP-A-61-24344.
It is described in Japanese Patent Publication No. 9. Examples of thermal polymerization initiators include azo compounds (eg, azobis (isobutyronitrile), 1,
1'-azobis (1-cyclohexanecarbonitrile)
And peroxides. The photopolymerization initiator is a compound capable of generating a free radical that can be added to the polymerizable compound upon exposure to light. Regarding the photopolymerization initiator, see Oster et al., "Chemical Review", No. 68.
125-151, Volume (1968), by Kosar, "Ligh
t-Sensitive System "(John Wiley & Sons, 1965
Pp. 158-193, JP-A-61-75342 and JP-A-2-207254.
Examples of the photopolymerization initiator include carbonyl compounds, halogen-containing compounds, redox couples of photoreducible dyes and reducing agents, organic sulfur compounds, peroxides, optical semiconductors and metal compounds. The polymerization initiator is preferably used in the range of 0.001 to 0.5 g, and more preferably 0.01 to 0.2 g, per 1 g of the total amount of the polymerizable compound and the crosslinkable polymer.

[Polymerizable Compound] As the polymerizable compound,
A compound capable of addition polymerization by free radicals, particularly a compound having an ethylenically unsaturated group (monomer or oligomer) is used. The polymerizable compound is described in JP-A-5-249667. 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 pentaerythritol tetraacrylate, trimethylolpropane triacrylate,
Mention may be made of dipentaerythritol hexaacrylate, polyester acrylates and polyurethane acrylates. The polymerizable compound is contained in the curable layer in an amount of preferably 3 to 90% by weight, more preferably 15 to 60% by weight, based on the total amount of the layer. You may use together 2 or more types of polymerizable compounds.

[Polymer contained in the curable layer] The curable layer contains a crosslinkable polymer. A non-crosslinkable polymer may be used in combination with the crosslinkable polymer. As the crosslinkable polymer, a polymer having an ethylenically unsaturated group in the main chain or side chain of the molecule is preferably used. The crosslinkable polymer may be a copolymer. Examples of polymers having an ethylenically unsaturated group in the main chain of the molecule include poly-
Mention may be made of 1,4-butadiene, poly-1,4-isoprene, natural and synthetic rubber. Examples of polymers having an ethylenically unsaturated group in the side chain of the molecule include poly-1,2-butadiene and poly-1,2-isoprene.

Further, a polymer of an ester or amide of acrylic acid or methacrylic acid, to which a specific residue (R group of --COOR or --CONHR) is bonded, can be used as the crosslinkable polymer. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ¹ = CR ² R
³ ,-(CH ₂ O) _n -CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ CH ₂ O) _n -CH ₂ CR ¹ = CR ²
R ³ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ¹ = CR ² R ³ ,-(CH ₂ ) _n -O-CO-CR ¹
= CR ² R ³ and-(CH ₂ CH ₂ O) ₂ -X (R ^{1 to} R ³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, or aryl. Is an oxy group, R ¹ and R ² or R ³ may combine with each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue). Can be mentioned. Specific examples of the ester residue, -CH ₂ CH = CH ₂ (JP 64-17
(Corresponding to the polymer of allyl (meth) acrylate described in JP 047), -CH ₂ CH ₂ O-CH ₂ CH = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ ,
-CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCO
O-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue) are included. Specific examples of amide residues include -C
H ₂ CH = CH ₂ , -CH ₂ CH ₂ -1-Y (Y is a cyclohexene residue) and -CH ₂ CH ₂ -OCO-CH = CH ₂ are included.

In the crosslinkable polymer as described above, free radicals (polymerization initiation radicals or growing radicals during the polymerization process of the polymerizable compound) are added to its unsaturated bond group to directly polymerize or polymerize the polymerizable compound. Addition polymerization is carried out through chains, and crosslinks are formed between polymer molecules to cure. Alternatively, atoms in the polymer (eg, hydrogen atoms on the carbon atom adjacent to the unsaturated bond group) are abstracted by free radicals to form polymer radicals, which bond to each other to form crosslinks between polymer molecules. Is cured.

Examples of non-crosslinkable polymers (polymers that are not crosslinkable or weakly crosslinkable) are polyacrylic acid ester, polymethacrylic acid ester, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, Polymethacrylonitrile, polyethylene,
Polyvinyl pyridine, polyvinyl imidazole, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, chlorinated polyethylene, chlorine polypropylene,
Polyester, polyamide, polyurethane, polycarbonate, ethyl cellulose, triacetyl cellulose,
Mention may be made of diacetyl cellulose and cellulose acetate butyrate. Among the repeating units of these polymers, copolymerizable units can be arbitrarily combined and used as a copolymer. 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 uncured curable layer is eluted and removed with an alkaline aqueous solution after curing, the (crosslinkable or non-crosslinkable) polymer used for the curable layer 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. Specifically, monomers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride can be copolymerized at the time of synthesizing the above-mentioned polymer to incorporate these acidic groups into the polymer of the curable layer. The molar content of the monomer having an acidic group in the copolymer is preferably 1 to 60%, more preferably 5 to 40%. The polymer of the curable layer is most preferably a copolymer obtained by copolymerizing the above-mentioned monomer having a crosslinkable group and a monomer having an acidic functional group. The molecular weight of the polymer of the curable layer is preferably in the range of 1,000 to 500,000.
You may use together 2 or more types of polymers. The content of the polymer in the curable layer is 10 to 90% by weight based on the whole curable layer.
Is preferable, and more preferably 30 to 80% by weight.

[Hydrophilic polymer] Photosensitive layer of photosensitive material,
The hydrophilic layer such as the overcoat layer or the image formation promoting layer contains a hydrophilic polymer as a binder. 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, sulfo, sulfonamide group, sulfonimide and amide. 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.
A water-swellable polymer has an affinity for water,
It does not completely dissolve in water due to the cross-linked structure of the polymer. As the water-soluble or water-swellable polymer, natural, synthetic or semi-synthetic polymer compounds can be used. Regarding the hydrophilic polymer, JP-A-5-2496
No. 67 publication. Polyvinyl alcohol is a particularly preferred hydrophilic polymer. Polyvinyl alcohol having various degrees of saponification can be used. However, in order to reduce the oxygen permeability, the saponification degree is preferably 50% or more, more preferably 80% 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. Examples of copolymerizable monomers include ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, methyl methacrylate and acrylamide. Further, post-modified polyvinyl alcohol can also be used. The post-modification is a method in which a compound having reactivity with a hydroxyl group of polyvinyl alcohol is used and then modified by a polymer reaction after the 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 the cross-linking agent, an aldehyde, a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid or an inorganic cross-linking agent (eg boric acid, titanium, copper) can be used. 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.
It is preferably from 05 to 20 g / m ² , and more preferably from 0.1 to 10 g / m ² . When gelatin is used in combination with another hydrophilic polymer in the layer containing silver halide, the pH of the layer containing silver halide is
Is preferably adjusted to a value of 1.2 or lower or 1.2 or higher than the isoelectric point of gelatin.

[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 is preferably one that releases a base at 50 to 200 ° C, and more preferably one that releases a base at 80 to 160 ° C. The base and the base precursor can be used in combination. The base or base precursor is 0.1 per mol of silver halide.
It is preferably used in the range of 20 to 20 mol, 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 the heat development and perform the heat development treatment 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, ethylene glycol, polyethylene glycol), polyhydric alcohols (eg, glycerin, butanediol, hexanediol), sugars, formate esters, ureas (eg, urea, diethylurea). , Ethylene urea, propylene urea), urea resin, phenol resin,
Examples thereof include amide compounds (eg, acetamide, propionamide), sulfamides and sulfonamides. 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 , and the addition amount is 0.1.
It is more preferably 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 cured image. As the colorant, known pigments and dyes can be used as long as they do not significantly impair the curing reaction of the curable layer or significantly impair the photosensitivity and developability of silver halide. When using a colorant for the purpose of preventing halation or coloring the image,
It is preferably added to the curable 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 the colorant, pigments or dyes described in JP-A-5-249667, "Color Index Handbook", and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, 1970) can be used. Dyes for preventing irradiation which have little influence on sensitivity are disclosed in Japanese Examined Patent Publication No. 41-20389 and 4
No. 3-3504, No. 43-13168, and Japanese Patent Laid-Open No. Hei 2
-39042 and U.S. Pat. No. 3697037.
No. 3,423,207, British Patent Nos. 1030392 and 1100546. The content of the colorant is preferably 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 azoles and azaindenes (Research Disclosure N.
o. 17643, pages 24 to 25 (1978)), nitrogen-containing carboxylic acids and phosphoric acids (described in JP-A-59-168442), cyclic amides (described in JP-A-61-151841), thioethers (special JP-A-62-151842), polyethylene glycol derivative (JP-A-62-151843), thiol (JP-A-62-151844), acetylene compound (JP-A-62-87957). ) And sulfonamide (JP-A-62-1782).
No. 32 publication). An aromatic ring (carbon ring or heterocycle) mercapto compound is also preferably used as an antifoggant or a development accelerator. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are preferred. The mercapto compound may be added to the photosensitive material as a mercapto silver compound (silver salt). 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] A matting agent may be added to the back layer or the uppermost layer of the light-sensitive material for the purpose of lowering the tackiness of the front surface or the back surface of the light-sensitive material and preventing adhesion when the light-sensitive materials are stacked. it can. As the matting agent, inorganic or organic solid particles that can be dispersed in a hydrophilic polymer are used. Such grains are well known in the ordinary silver salt photography art. Examples of materials for the matting agent include oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers. The particle size of the matting agent is 1 to 50 μm
Is preferred. Matting agent is 0.01 to 1 g / m
It is preferable to use within the range of ² , 0.1 to 0.7 g
It is more preferable to use in the range of / m ² .

[Polymerization Inhibitor] A polymerization inhibitor may be added to the curable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. Conventionally known polymerization inhibitors can be used. Examples of the polymerization inhibitor include nitrosamine compounds, urea compounds, thiourea compounds, thioamide compounds, phenol derivatives and amine compounds.

[Image exposure] Image exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity of silver halide (sensitizing dye) which is a photosensor. Examples of light sources include tungsten lamps, halogen lamps, xenon lamps,
Lamps such as xenon flash lamps, mercury lamps, carbon arc lamps, various lasers (eg semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers), light emitting diodes,
A cathode ray tube etc. can be mentioned. 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 generally 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.

In general, the exposure process of silver halide, that is, the process of forming a latent image is affected by the temperature and humidity during exposure,
It is known that the sensitivity of photosensitive materials changes. Therefore, it is desirable that the temperature and humidity of the atmosphere of the light-sensitive material and the light source at the time of exposure are controlled within a constant range as much as possible. Specific adjusting means of the image recording apparatus for achieving the above object is disclosed in JP-A-3-63143 and JP-A-3-63143.
It is described in each publication of No. -63637. In particular,
It is preferable to set one point in the range of 5 to 40 ° C. (preferably 10 to 35 ° C.) as the set temperature and control the temperature within ± 5 ° C. from the set temperature. It is preferable to similarly control the atmospheric humidity in the apparatus including the photosensitive material and the optical system. The humidity is preferably in the range of 10 to 80% (relative humidity), more preferably in the range of 15 to 75%, most preferably in the range of 25 to 70%.

[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 in 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 opened to the air and heated, oxygen in the air may permeate into the light-sensitive material and interfere with the polymerization reaction. It is preferable to use a polymer having a low viscosity as the binder. The heating temperature is 60 to 200 ° C., more preferably 100 to 15
It is in the range of 0 ° C. The heating time is in the range of 1 to 180 seconds, more preferably 5 to 60 seconds.

The light-sensitive material may be exposed before or after the exposure.
Preheat at a temperature higher than the main heating temperature for a short time, or
Alternatively, post-heating may be performed after main heating. Pre-heating or post-heating can improve the sensitivity and the curing degree of the image. The post-heating may be performed after the image formation post-treatment, for example, after the elution (etching) treatment. When a cured 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, radicals can be generated by heating at the time of thermal development, so heating is required only once. 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 dose is 10 ^{3 to} 10 ⁷ ergs /
It is in the range of cm ² .

[Removal Step] In the removal step, there are a method using an eluate and a method using a removal sheet. First, the method using the eluate will be described. As the eluent (or etching solution) for removing the uncured portion, any solvent can be used as long as it can remove the uncured portion of the curable layer.
Preferably an alkaline solvent is used. The alkaline solvent is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent. As the alkaline compound, various organic and inorganic compounds can be used. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, ammonia and amino alcohols (eg, Monoethanolamine, diethanolamine, triethanolamine).
As the solvent of the eluate, water or various organic solvents can be used as described above. The solvent of the eluate is preferably mainly composed of water. The eluent mainly composed of water,
An organic solvent can be added if necessary. As the organic solvent, alcohols or ethers are preferable.
Examples of alcohols include lower alcohols (eg, methanol, ethanol, propanol, butanol), alcohols having an aromatic group (eg, benzyl alcohol,
Examples thereof include phenethyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol) and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine).
Examples of ethers include cellosolves. The eluate may contain a surfactant, an antifoaming agent, and other various additives as required.

Next, a method of using the removal sheet will be described. When the removal sheet is brought into close contact with the surface of the curable layer, the adhesive force between the interface between the curable layer and the removal sheet becomes different between the uncured portion and the cured portion. Whether the cured part is transferred or the uncured part is transferred depends on the properties of the crosslinkable polymer or the polymerizable compound, the amount of the crosslinkable polymer or the polymerizable compound added, the properties of other components in the curable layer, and the like. The amount of addition, etc., and various conditions of the removal process (heating temperature, time,
It may vary depending on the pressurizing temperature, etc.). As a result of the above, the cured portion or the uncured portion selectively remains in an image form. When the curable layer contains a coloring material, a color image is formed on the photosensitive material.

[Transfer Processing] In the transfer processing, the cured image is transferred by adhering it to another sheet (image receiving material). 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 attached to the cured image to visualize the image. It is also possible to provide an adhesive layer on the photosensitive material, selectively remove the uncured 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 cured portion is selectively transferred.

[Dyeing process] The cured image is dyed to visualize the image. You may perform dyeing processing with respect to the image receiving material which transferred the cured image. The image obtained as described above can be used for printing plates, color proofs, hard copies, reliefs and the like.

[0058]

【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 a rectangular wave alternating waveform current (conditions: voltage at anode 12.7 v, ratio of electricity at cathode to electricity at anode was 0.9, electricity at anode was 160 coulomb / dm ² ). Then, electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution containing 0.5% aluminum nitrate. 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 seconds and then treated in a 30% aqueous sulfuric acid solution at 55 ° C. for 1 minute. Next, so that the thickness becomes 2.5 g / dm ² ,
Current density 2A using direct current in 20% sulfuric acid aqueous solution
Anodizing treatment was performed under the condition of / dm ² . The obtained aluminum plate was washed with water and dried to prepare a support.

[Formation of Curable Layer] The following coating liquid was applied onto the above support using a whiler and dried to form a curable layer having a dry film thickness of about 1.3 μm.

──────────────────────────────────── Curable layer coating liquid ────── ────────────────────────────── Oily substances shown in Table 1 Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80 / 20) 20% by weight propylene glycol monomethyl ether solution 37.5 g Pigment dispersion liquid 13.0 g Propylene glycol monomethyl ether 65.5 g Methyl ethyl ketone 95.5 g ───────────────── ────────────────────

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

[0062]

[Table 1] Table 1 (Unit: g) ──────────────────────────────────── Sample number 1 2 3 4 5 6 7 ──────────────────────────────────── Polymerizable compound 2.5 1 .5 1.5 1.5 1.5 1.5 --- Tricresyl phosphate --- 0.6 0.3 --- 0.75 Dibutyl phthalate --- --0.6 --- ─────────── ────────────────────────── Note: Polymerizable compound = pentaerythritol tetraacrylate

[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. to 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) A potassium bromide aqueous solution containing an acid salt was added in two stages by a double jet method to prepare a core / shell type silver iodobromide emulsion having the following composition.

[0064]

[Chemical 1]

Core: silver iodobromide (silver iodide content: 7.5 mol%) Shell: pure silver bromide Core / shell: 3/7 (silver mol ratio) Average silver iodide content: 2.55 Mol% Average particle size: 0.30 μm

The obtained emulsion grains were monodisperse, and 98% of the total number of grains were present within ± 40% of the average grain size. Then, this emulsion was desalted, and then a solution of the following spectral sensitizing dye in methanol (10 ^-2 M / liter) was added to an emulsion corresponding to 1 mol of silver nitrate (incubated at 40 ° C, after stirring).
Then, 00 ml was added, the pH was adjusted to 6.5 and the pAg was adjusted to 8.3 to prepare a silver halide emulsion.

[0067]

[Chemical 2]

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

[0069]

[Chemical 3]

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

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol with a saponification degree of 81.5% (PVA-405, manufactured by Kuraray Co., Ltd.) 10% by weight aqueous solution 42.0 g of the above reducing agent dispersion 8.0 g 0.1% by weight methanol solution of the following additives 5.5 g 0.5% by weight aqueous solution of potassium bromide 1.7 g of the above halogenation Silver emulsion 2.8g 5% by weight aqueous solution of the following surfactant 2.7g Water 70.7g ───────────────────────────── ────────

[0072]

[Chemical 4]

[0073]

[Chemical 5]

[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). The particle size of the base precursor was about 0.5 μm or less.

[0075]

[Chemical 6]

[Formation of Image Formation Accelerating Layer] The following coating solution was prepared, coated on the above-mentioned photosensitive layer and dried to form an image forming 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% (trade name: PVA-205, Kuraray ( Co., Ltd.) 10% by weight aqueous solution 100.0 g The above base precursor dispersion 3.8 g 5% by weight aqueous solution of the above surfactant 2.0 g ────────────────── ────────────────────

(Image formation) A 200 lpi halftone image original and a bandpass filter (transmitting light having a wavelength of about 500 nm) were brought into close contact with the light-sensitive material obtained as described above,
0.8 at 3 lux intensity using a tungsten lamp
After image exposure for 2 seconds, the support side of the photosensitive material was brought into close contact with a heating plate heated to 145 ° C., and the thickness of the photosensitive material was about 1
Thermal development was performed for a heating time shown in Table 2 in a state where a polyester film having a thickness of 00 μm was closely adhered and shielded from the air. Then, the photosensitive layer and the image formation accelerating layer were removed by washing with water, and an eluate (Fuji PS Developer DP manufactured by Fuji Photo Film Co., Ltd.) was used.
-4) was immersed at 30 ° C. for 1 minute, etched, and washed with water. The curable layer in the unexposed area was eluted and removed, and a red-colored polymer image was formed in the exposed area.

Table 2 shows the reflection density (fog density) of the non-image area and the reproduction area of the halftone image at each heat development time.
The reflection density is a value measured with green light. When there is no fog (concentration of the support itself), it is 0.3.

[0080]

[Table 2] Table 2 ──────────────────────────────────── Sample oily heat development time number substance Measurement items 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds ──────────────────────────────────── M Yes Fog density 0.3 0.3 0.3 0.4 0.4 0.7 1 Shadow 98% 97% 90% 80% -O No highlight 2% 1% 1% 1% − ────────── ─────────────────────────── M Yes Fog density 0.3 0.3 0.4 0.4 0.9 1.2 2 Shadow 98% 97% 85% − − O No highlight 2% 1% 1% − − ───────────────────────────────── ──── M Yes Fog density 0.3 0.3 0.3 0.3 0.3 0 3 3 Shadow 99% 97% 98% 97% 97% O Yes Highlight 2% 1% 2% 1% 1% ──────────────────────── ───────────── M Yes Fog density 0.3 0.3 0.3 0.3 0.3 0.4 4 Shadow 98% 97% 96% 90% -O Yes Highlight 2% 1 % 1% 1% − ────────────────────────────────────M M Yes Fog density 0.3 0 .3 0.3 0.3 0.3 0.35 Shadow 98% 97% 97% 96% 97% O Yes Highlight 2% 2% 1% 1% 1% ────────────── ─────────────────────── 6 MO No fog density 0.5 0.5 0.5 0.7 1.0 1.2 1.2 ──────── ────────────────── ─────────── M No fog density 0.3 0.3 0.3 0.3 0.3 0.3 7 Shadow-98% 98% 98% 97% O Yes Highlight-3% 2% 2% 2% ──────────────────────────────────── Note: M = Polymerizable compound (pentaerythritol Tetraacrylate) O = non-polymerizable oily substance

When the curable layer does not contain the non-polymerizable oily substance (O), fog is likely to occur, and the shadow portion is easily crushed as the heat development time increases. On the other hand, when the non-polymerizable oily substance is contained, fogging is less likely to occur and the shadow portion is less likely to be crushed.

Example 2 A photosensitive material of Sample No. 8 was prepared in the same manner as in the preparation of the photosensitive material of Sample No. 2 of Example 1, except that the coating solution for the photosensitive layer was changed to the following composition. .

──────────────────────────────────── Photosensitive layer coating liquid ────── ────────────────────────────── Polyvinyl alcohol with a saponification degree of 81.5% (PVA-405, manufactured by Kuraray Co., Ltd.) 10% by weight aqueous solution 40.0 g Dibutyl phthalate 1 g was emulsified in 10% aqueous solution 10% of polyvinyl alcohol (PVA-405) 2.3 g Reducing agent dispersion liquid used in Example 1 8.0 g Example 0.1 wt% methanol solution of the additive used in 1 5.5 g 0.5 wt% aqueous solution of potassium bromide 1.7 g Silver halide emulsion used in Example 1 2.8 g Interface used in Example 1 5% by weight aqueous solution of activator 2.7 g water 70.7 g ─────────────────── ──────────────────

An image was formed on a light-sensitive material and evaluated in the same manner as in Example 1. The results are shown in Table 3.

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[Table 3] Table 3 ──────────────────────────────────── Sample heat development time number Measurement item 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds ──────────────────────────────────── Fog density 0. 3 0.3 0.3 0.3 0.3 0.3 8 Shadow 99% 98% 98% 98% 98% Highlight 2% 2% 2% 1% 1% ────────────── ───────────────────────

Claims (1)

[Claims] 1. A support is provided with two or more layers containing a silver halide, a reducing agent and a crosslinkable polymer,
A light-sensitive material in which a photosensitive layer containing silver halide and a curable layer containing a crosslinkable polymer are separately provided, and one of the layers contains a non-polymerizable oily substance. material.