JPH0627652A - Photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material capable of giving a high contrast image, having satisfactory preservability and produced at a low cost as a photosensitive material utilizing the photosensitivity of silver halide and forming an image by efficient polymn. of a polymerizable compd. by heating. CONSTITUTION:When a photosensitive polymerizable layer contg. silver halide, a reducing agent and a polymerizable compd. is formed on a substrate to obtain a heat developable photosensitive material, a substance which dissolves in water by >=0.1wt.% is used as the reducing agent. This reducing agent is preferably a compd. represented by a formula R<1>-NHNHCO-R<2>-X, wherein R<1> is optionally substd. alkyl, aryl or a heterocyclic group, R<2> is optionally substd. alkylene, arylene or a divalent heterocyclic group and X is a hydrophilic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material which forms an image by utilizing the photosensitivity of silver halide and efficiently polymerizing a polymerizable compound.

[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 No. 17206).
65 and British Patent 1131200), 47-2.
0741, 49-10697, JP-A-57-13.
8632, 57-142638, 57-176.
033, 57-21146, 58-1075.
No. 29, No. 58-121031, No. 58-16914
No. 3, No. 61-59062, No. 61-73145,
No. 61-183640, No. 61-188535 and No. 61-228441. The light-sensitive material used in this image forming method usually has a photosensitive polymerizable layer containing a silver halide, a reducing agent and a polymerizable compound on a support.

In this method, the polymerization is carried out by an oxidant radical of a reducing agent that has reduced silver halide (a radical generated by decomposition of an oxidant of a reducing agent; hereinafter referred to simply as oxidant radical). Be started. Therefore, it is advantageous to dispose the reducing agent and the silver halide in positions as close to each other as possible because the radical generation efficiency is increased. In addition, since a certain reducing agent itself or its oxidant has a polymerization inhibiting effect, it is preferable to separate the layer in which the polymerization reaction proceeds from the layer in which the radical generation reaction occurs.

[0004]

However, lipophilic ones have been conventionally used as reducing agents that cause efficient polymerization. In order to allow the lipophilic reducing agent to be present in the layer containing the silver halide, which is a hydrophilic colloid, it is necessary to perform a complicated operation such as dispersing it as a solid or dissolving it in dispersed oil droplets, which increases the manufacturing cost. It was one of the causes. Further, even when it is contained in the hydrophilic layer in this way, the reducing agent may move to another lipophilic layer during storage, which may reduce the polymerization efficiency.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material which can provide a high-contrast image in the above-mentioned image forming system, has good storability, and has a low manufacturing cost.

[0006]

SUMMARY OF THE INVENTION The above object of the present invention is to provide a heat-developable light-sensitive material of the present invention, which comprises a support and a light-sensitive and polymerizable layer containing a silver halide, a reducing agent and a polymerizable compound. The heat-developable light-sensitive material can be achieved by the above-mentioned reducing agent being a substance that dissolves in water in an amount of 0.1% by weight or more.

The preferred embodiments of the present invention are shown below. [1] A photosensitive material in which the reducing agent is a compound represented by the following formula (1).

[Chemical 2] In the formula (1), R ¹ represents an optionally substituted alkyl group, aryl group or heterocyclic group, and R ² represents an optionally substituted alkylene group, arylene group or divalent heterocyclic group. , X represents a hydrophilic group. [2] In the formula (1), R ¹ represents an optionally substituted alkyl group, aryl group or heterocyclic group, and R 1
² is a photographic material in which an alkylene group which may be substituted, an arylene group or a divalent heterocyclic group is represented, and X is a carboxyl group or a salt thereof or a sulfonic acid group or a salt thereof. [3] A plurality of layers in which the photosensitive polymerizable layer includes a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound (that is, a polymerizable monomer and / or a crosslinkable polymer). And a reducing agent contained in at least one layer of the plurality of layers. [4] A photosensitive material in which a photosensitive polymerizable layer composed of a plurality of layers and an overcoat layer are provided on a support, and the reducing agent is contained in at least one of these layers. [5] A photosensitive material in which the reducing agent is contained in the photosensitive layer of the photosensitive polymerizable layer composed of the plurality of layers. [6] A photosensitive material in which the polymerizable layer of the photosensitive polymerizable layer composed of the plurality of layers is lipophilic, the photosensitive layer is hydrophilic, and the photosensitive layer contains the reducing agent. . [7] A photosensitive material in which the overcoat layer is made of a binder polymer having low oxygen permeability. [8] A photosensitive material in which polyvinyl alcohol having a low saponification degree is used as the binder polymer of the photosensitive layer. [9] A light-sensitive material containing a thermal development accelerator in at least one layer. [10] A photosensitive material in which the polymerizable layer contains a polymer having an acidic group. [11] A light-sensitive material containing a base precursor in at least one layer.

[0008]

INDUSTRIAL APPLICABILITY The light-sensitive material of the present invention using a water-soluble reducing agent can give an image with high contrast, has good storability, and has a low manufacturing cost. In particular, the light-sensitive material of the present invention using the compound represented by the above formula (1) as a reducing agent has excellent properties.

In the light-sensitive material of the present invention, a photosensitive polymerizable layer containing silver halide, a water-soluble reducing agent and a polymerizable compound is provided on a support. In the present specification, the water-soluble reducing agent refers to an agent that dissolves in water at 4 ° C in an amount of 0.1% by weight or more. The water-soluble reducing agent used in the present invention is preferably dissolved in water in an amount of 1% by weight or more.

The layer constitution and each component of the light-sensitive material of the present invention will be described in detail below.

[Reducing agent] The reducing agent is used in the range of 0.1 to 10 mol, and more preferably in the range of 0.5 to 5 mol, per mol of silver halide.

The reducing agent used in the present invention is preferably a compound represented by the above formula (1). In the formula (1), R ¹ represents an optionally substituted alkyl group, aryl group or heterocyclic group, and R ² represents an optionally substituted alkylene group, arylene group or divalent heterocyclic group. , X represents a hydrophilic group. X is preferably a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof. In addition to X, there may be a substituent of R ² corresponding to X. Therefore, R ²
The number of the hydrophilic substituents X bonded to is only one, and there may be two or more. Preferably, the number of hydrophilic substituents is 1 to 3.

The compound represented by the above formula (1) will be described in more detail. R ¹ in the formula (1) is
A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isoamyl, isohexyl, neopentyl and t-butyl (in the case of a substituted alkyl group, the substituent is hydroxy). Group, carboxyl group, sulfonic acid group, alkoxy group having 1 to 12 carbon atoms, cyano group, amino group, alkylamino group having 1 to 12 carbon atoms, halogen atom, aryl group having 6 to 15 carbon atoms, from 1 carbon atom Examples include a 16-amide group, a C1-C16 urea group and a C1-C16 thiourea group); phenyl, naphthyl, anthryl, biphenyl,
Substituted or unsubstituted aryl groups such as terphenyl and indene, fluorene, acenaphthene, perylene, fluorenone, anthrone, anthraquinone, benzanthrone, monovalent groups derived from isocoumarin and the like (in the case of a substituted aryl group, a substituent is, Examples thereof include the substituents exemplified as the substituent of the substituted alkyl group, an alkyl group having 1 to 12 carbon atoms, a nitro group, a trifluoromethyl group, etc. However, the position and the number of the substituents are not particularly limited. ); Or substituted or unsubstituted heterocycles derived from pyridine, quinoline, oxazole, thiazole, oxadiazole, benzoxazole, benzimidazole, benzothiazole, benzotriazole, dibenzofuran, carbazole, xanthene, maleinimide, etc. (When substituted, the substituents may be mentioned as examples are the same as those of the substituent of the substituted aryl group) valent group represent.

R ² in the formula (1) may be a divalent group corresponding to the above R ¹ . That is, a substituted or unsubstituted alkylene group having 1 to 18 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene, and hexylene (when substituted, the substituent is exemplified as the substituent of the substituted alkyl group for R ¹ described above. And a hydrophilic substituent such as a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof); phenylene, naphthylene and terphenylene and indene, fluorene, acenaphthene, perylene, fluorenone, anthrone, A substituted or unsubstituted arylene group such as a divalent group derived from anthraquinone, benzanthrone, isocoumarin or the like (when substituted, the substituent is exemplified as the substituent of the substituted aryl group for R ¹ , and Carboxyl group or its salt, Examples thereof include hydrophilic substituents such as a rufonic acid group or a salt thereof); or pyridine, quinoline, oxazole, thiazole, oxadiazole,
A substituted or unsubstituted divalent group derived from a heterocycle such as benzoxazole, benzimidazole, benzothiazole, benzotriazole, dibenzofuran, carbazole, xanthene, and maleinimide (when substituted, the substituent is the above-mentioned R ¹ as an example of the substituent of the substituted aryl group of ¹ , and an aqueous substituent such as a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, etc.) can be exemplified.

X in the formula (1) is a carboxyl group,
Alkali metal cations such as Na ⁺ , K ⁺ , Li ⁺ , NH
Examples thereof include salts with ammonium ions such as ₄ ⁺ , sulfonic acid groups, and salts of sulfonic acid groups with the above cations. Further, X is not only directly bonded to R ² but also R ²
It may be bonded to the substituent.

Specific examples of the reducing agent are shown below, but the present invention is not limited thereto.

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

These compounds are referred to as "Beilstein" No. 4
It can be easily synthesized by a known method as described in ed. 15/1, p.163. Next, as a representative example, a synthesis example of the compound (A) will be shown.

(Synthesis example) Synthesis of compound (A) A solution obtained by dissolving 98.2 g (0.909 mol) of phenylhydrazine in 500 ml of acetone was added with 50 g of 2-chloro-4-nitrobenzoyl chloride under water cooling.
It was dripped in 0 minutes. After standing overnight, the reaction mixture was poured into 3.5 liters of water containing 100 ml of concentrated sulfuric acid, and the resulting crystals were collected by filtration. The obtained crystals were recrystallized from ethanol to obtain 1-phenyl-2- (2-chloro-4-nitrobenzoyl) hydrazine (35.88 g, yield 54.2%) as yellow crystals. Mp: as 181-184 ° C. Elemental analysis _{C 13 H 10 Cl 1 N 3} O 3, Calcd C: 53.53% H: 3.46% N: 1
4.41% Actual value C: 53.43% H: 3.45% N: 1
4.21%

Next, 32.1 g (0.11 m) of the above crystal.
ol) and DMF393 ml, water 50 ml, hydrochloric acid 18.8.
ml and iron 30.8 g were mixed and stirred at 100 ° C. for 1 hour. After neutralization with saturated NaHCO ₃ water, filtration was performed, the filtrate was poured into 5 liters of water, and the resulting crystals were collected by filtration to give 1-phenyl-2- (2-chloro-4-aminobenzoyl) hydrazine 26 0.42 g (yield 91.8%) was obtained as white crystals. Melting point: 208-211 ° C. Elemental analysis value Calculated value as C ₁₃ H ₁₂ Cl ₁ N ₃ O C: 59.66% H: 4.63% N: 1
6.06% Actual value C: 59.54% H: 4.61% N: 1
6.02%

2.96 g of phthalic anhydride (20 mmo
1-phenyl-in a solution prepared by dissolving l) in 50 ml of DMF.
5.23 g of 2- (2-chloro-4-aminobenzoyl) hydrazine was added, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into 500 ml of water, and the generated crystals were collected by filtration and dried to obtain 6.69 g of compound (A) (yield 81.7%) as white crystals. Decomposition point (dehydration): 184 ° C. Elemental analysis value C ₂₁ H ₁₆ Cl ₁ N ₃ O ₄ Calculated value C: 61.55% H: 3.94% N: 1
0.25% measured value C: 61.36% H: 3.95% N: 1
0.12%

[Layer Constitution of Photosensitive Material] The layer constitution of the photosensitive material of the present invention may be a single layer structure in which all necessary components are contained in one layer, or a polymerizable photosensitive layer, an overcoat layer and an image forming layer. It may have a multi-layer structure including a promotion layer and the like. Such a layer structure can be determined according to the application. However, the photosensitive polymerizable layer containing the above silver halide, reducing agent and polymerizable compound (polymerizable monomer and / or crosslinkable polymer) is a photosensitive layer containing silver halide and a polymerizable compound containing a polymerizable compound. It is preferably composed of two layers, a layer and a layer. Further, the light-sensitive material of the present invention comprises a photosensitive layer containing silver halide, a polymerizable layer containing a polymerizable compound, and an image-forming promoting component containing an image-forming promoting component such as a reducing agent, a base, a base precursor or a thermal development accelerator. It is preferred to have at least 3 layers. The order of laminating these layers varies depending on the purpose of use, but when used in a printing plate, for example, it is preferable that a polymerizable layer, a photosensitive layer, and an image formation promoting layer are provided in this order on a support.

The polymerizable layer is cured by the polymerization and / or crosslinking of the polymerizable monomer and / or the crosslinkable polymer caused by radicals (or other active species). The polymerizable layer is composed of a polymerizable compound and a binder polymer (a colorant if necessary). The thickness of the polymerizable layer can be determined according to the application. However, if it is too thin, the strength of the obtained image will be low, and if it is too thick, it will be difficult to cure it to the bottom of the layer. Preferably 0.1-
20 μm, more preferably 0.3 to 7 μm, and further preferably 0.5 to 10 μm. The coating amount of the polymerizable compound is 0.03 to ² g / m ² , more preferably 0.1.
Is in the range of 1.0 g / m ² . Further, the coating amount of the binder polymer is in the range of 0.1 to 7 g / m ² , more preferably 0.3 to 3 g / m ² .

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 photosensitive layer preferably further contains a hydrophilic binder polymer. The layer thickness of the photosensitive layer is preferably in the range of 0.1 to 20 μm, more preferably 0.5 to 10 μm.

If necessary, an overcoat layer or an image formation accelerating layer can be further provided on the photosensitive layer. These layers typically include hydrophilic polymers. However, it is also possible to use hydrophobic polymers. For example, a hydrophobic polymer can be dissolved in a solvent and applied, or a polymer latex can be applied. In this case, these layers are peeled and removed after thermal development and prior to etching. The overcoat layer protects the light-sensitive material and prevents the ingress of oxygen in the air to enhance the degree of curing of the polymerizable layer. Further, the image formation promoting layer, the overcoat layer contains a component that promotes image formation (eg, a base or a base precursor, a reducing agent, a thermal development accelerator), while promoting the image formation, Generally, it also functions as the above-mentioned overcoat layer. These layers can contain a matting agent. The matting agent reduces the tackiness of the layer surface and prevents adhesion when the light-sensitive materials are stacked. The layer thickness of these layers is in the range of 0.3 to 20 μm, more preferably 0.5 to 10 μm.

Between each layer or between the support and the coating layer,
An intermediate layer can be provided. The intermediate layer functions as, for example, an antihalation layer containing a colorant and a barrier layer that prevents components from moving between layers and diffusing or mixing during storage of the photosensitive material. The material of the intermediate layer can be determined according to the application. For example, a hydrophilic polymer used in the photosensitive layer or the overcoat layer can be used. The layer thickness of the intermediate layer is preferably about 10 μm or less.

[Support] As the material of the support used in the present invention, paper, synthetic paper, paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide) , Nylon, cellulose triacetate), metal plates (eg, aluminum, aluminum alloys, zinc, iron, copper), and papers and plastic films laminated or vapor-deposited with these metals.

When the light-sensitive material of the present invention is used for a lithographic printing plate, the material for the support is preferably an aluminum plate, polyethylene terephthalate film, polycarbonate film, paper or synthetic paper. In addition, Japanese Patent Publication Sho 48-1832
A composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film as described in Japanese Patent No. 7 is also preferable. The paper support is described in JP-A-61-3797 and JP-A-61-112150.

As a typical example, the case where an aluminum plate is used as a support will be described below. The support is subjected to surface treatment such as surface roughening treatment (graining treatment) or surface hydrophilization treatment, if necessary.

The surface roughening treatment (graining treatment) is 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 electrolytic solution). And / or mechanical graining method (eg, wire brush grain method of scratching aluminum surface with metal wire, ball grain method of graining aluminum surface with abrasive ball and abrasive, nylon brush and abrasive agent) The brush grain method of making a grain on the surface).

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

Usually, after alkali etching, the aluminum plate is washed with an acid to remove stains (smuts) left on the surface. Preferable acids used at this time are nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid.

The smut removal treatment after the electrochemical graining treatment is carried out by contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C., which is described in JP-A No. 53-12739. It can be effectively carried out by the method described in JP-B-48-28123.

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 a solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., an anodized film is formed on the aluminum surface by applying a direct current or an alternating current to the aluminum plate. . 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., the current density is 0.5 to 60 amperes / dm ² , and the voltage is 1 to 100.
v, the electrolysis time is preferably in the range of 10 to 100 seconds.

A particularly preferred anodic oxidation method is a method of anodic oxidation in sulfuric acid at a high current density (British Patent No. 1412768).
And a method of anodizing phosphoric acid as an electrolytic bath (described in US Pat. No. 2,511,661).
Is.

The anodized aluminum plate is treated with an alkali metal silicate (for example, the aluminum plate is immersed in an aqueous solution of sodium silicate), or the adhesion between the aluminum support and the polymerizable layer and the printing characteristics are improved. Therefore, an undercoat layer can be provided on the surface of the support.

The components constituting the undercoat layer include casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid, monoethanolamine, diethanolamine, triethanolamine, tripropanolamine and their hydrochloric acid. Salts, oxalates, phosphates, aminoacetic acids, monoaminomonocarboxylic acids such as alanine, serine, threonine, oxyamino acids such as dihydroxyethylglycine, sulfur-containing amino acids such as cysteine and cystine, aspartic acid, glutamic acid, etc. Monoaminodicarboxylic acid, diaminomonocarboxylic acid such as lysine, amino acid having aromatic nucleus such as p-hydroxyphenylglycine, phenylalanine and anthranil, sulfamic acid, cyclohexylsulfamim Aliphatic amino sulfonic acids such as acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyl iminodiacetic acid, hydroxyethyl ethylenediamine acetate, ethylenediamine diacetic acid,
(Poly) aminopolyacetic acid such as cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, etc. and some or all of the acid groups of these compounds have become salts such as sodium salt, potassium salt and ammonium salt Can be mentioned. These may be used in combination of two or more.

[Silver Halide] In the present invention, the silver halide includes silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like. If it is a silver halide consisting of chlorine, bromine, and iodide,
Any particles can be used.

The shape of silver halide grains is not limited to those having a regular crystal form such as a cube, octahedron and tetradecahedron, but those having an irregular crystal form such as a sphere and a plate.
It may have a crystal defect such as a twin plane, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains having a projected area diameter of up to about 10 microns. Further, a polydisperse emulsion or a monodisperse emulsion described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent No. 14,137,48 may be used, but an emulsion having high monodispersity is preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used. Tabular grains are
toff) "Photographic Science and
Engineering (Photographic Science and Engineer
ing) ", Vol. 14, pp. 248-257 (1970);
It can be easily adjusted by the method described in U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,121,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide.

The silver halide grains include copper, thallium,
Lead, bismuth, cadmium, zinc, chalcogen (eg, sulfur, selenium, tellurium), gold or a noble metal of Group VIII (eg, rhodium, iridium, iron, platinum, palladium) in the form of their respective salts according to a conventional method. It can be added by adding during or after grain formation.
The specific method is described in US Pat.
No. 951933, No. 2448060, No. 2628.
No. 167, No. 2950972, No. 3488709.
No. 3,373,313, No. 3772031, No. 4,269,927, and Research Disclosure (RD), Vol. 134, No. 13452
(June 1975).

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

Two or more kinds of silver halide grains having different halogen compositions, crystal habits and grain sizes may be used in combination.

The silver halide is preferably used in the form of 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 may be a negative type silver halide or an inversion type silver halide capable of directly obtaining a positive image.

The silver halide emulsion is usually prepared after physical ripening.
Chemical sensitization is performed, but chemical sensitization may not be performed.
However, it is preferred to use silver halide grains having a relatively low fog value. A light-sensitive material using such silver halide grains is described in JP-A-63-68830. 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. 18716
(See right column on page 648) for spectral sensitizers, see No. 17
643 (pages 23-24) and No. 18716 (648
In the right column on page-), for the supersensitizer, No. 18716
(Page 649, right column-), respectively. 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).

[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 is described in US Pat. No. 4,500,626.
Examples thereof include benzotriazoles, fatty acids and other compounds described in columns 2 to 53. Further, silver salts of carboxylic acids having an alkyl group such as silver phenylpropiolic acid described in JP-A-60-113235 and acetylene silver described in JP-A-61-290444 and 64-57256 are also useful. Is. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0 to 10 mol, preferably 0 to 1 mol, per 1 mol of silver halide. Further, instead of the organic silver salt, an organic compound constituting the organic silver salt may be added to the photosensitive layer and partially reacted with silver halide in the photosensitive layer to be converted into an organic silver salt.

[Polymerizable Compound] In the present invention, as the polymerizable compound, a polymerizable monomer or a crosslinkable polymer 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 its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid. Mention may be made of 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, dimethacrylate of polyoxyalkylenated bisphenol A, etc., wherein some or all of the acryloyl groups of the polymerizable monomer compounds listed as specific examples of the above acrylic acid esters are replaced with methacryloyl groups. A compound can be mentioned.

The polymerizable monomer can also be selected from commercially available products and used. As commercially available polymerizable monomers,
For example, Aronix M manufactured by Toagosei Kagaku Kogyo Co., Ltd.
-309, M-310, M-315, M-400, M
-210, M-6100, M-8030 and M-81
00, Kayarad HX-220 manufactured by Nippon Kayaku Co., Ltd.
HX-620, R-551, TMPTA, R-330,
DPHA, DPCA-60, R-712, R-310,
R-167, R-604 and R-684 are mentioned.

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 has a double bond group (A) to which a radical (polymerization initiation radical or growth radical in the polymerization process of a polymerizable monomer) can be added.
Polymers having a main chain or a side chain of the molecule, and (B) a polymer in which an atom (a halogen atom such as hydrogen atom or chlorine) of the main chain or a side chain is easily extracted to generate a polymer radical.

Examples of the above-mentioned polymer (A) include those described in JP-A No. 64-17047.
Polymers having an ethylenically unsaturated double bond in the side chain (eg, polymers of allyl (meth) acrylate (including copolymers), 1,2-polybutadiene, 1,2-polyisoprene) and unsaturated double bonds in the main chain A polymer having a bond (eg, poly-1,4-butadiene, poly-1,4-
Mention may be made of isoprene (including copolymers), natural and synthetic rubber.

Examples of the above-mentioned polymer (B) include:
The polymers described on pages 147 to 192 of “Polymer Reaction” (Journal of the Polymer Society of Japan / Kyoritsu Shuppan, 1978) can be mentioned. Specifically, poly (meth) 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, triacetyl cellulose, ethyl cellulose, polyvinyl pyridine, polyvinyl imidazole.

As will be described later, when the etching treatment is carried out 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, 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 copolymers, the molar content of monomers with acidic groups is in the range 1 to 50%, more preferably 5 to 30%.

The above-mentioned polymerizable compounds may be used alone or in combination of two or more kinds. Regarding a light-sensitive material in which two or more kinds of polymerizable compounds are used in combination, JP-A-62-
It is described in Japanese Patent Publication No. 210445. 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.
Needless to say, the use of a substance that also serves as a reducing agent and a polymerizable compound or a colorant and a polymerizable compound as described above is included in the embodiment of the light-sensitive material.

The polymerizable compound is contained in the polymerized 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.

[Binder of Polymerizable Layer] A binder may be further added to the polymerizable layer of the photosensitive material of the present invention in order to improve the strength. As a binder,
Natural and synthetic polymeric compounds can be used. Of these, oil-soluble ones are preferable. The molecular weight of the polymer is not particularly limited, but is preferably in the range of about 3000 to 500,000. 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. Therefore, the crosslinkable polymers described above can be and are preferably used as binders.

Specific examples of the binder include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), condensation polymerization type synthetic homopolymers and copolymers (eg, polyesters, polyamides). , Polyurethane, polyester-
Polyamide).

As will be described later, when the etching treatment is performed 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 1 to
It is in the range of 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.

As a binder or a polymerizable compound,
If a polymer having an ethylenically unsaturated double bond in the side chain is used, an image can be obtained even if the polymerizable layer does not contain a polymerizable monomer, but in general, it is preferable to use a polymerizable monomer in combination. It is preferable 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 not particularly limited as long as it does not interfere with the curing reaction of the polymerizable layer, but is 0 to 80% by weight, preferably 0 to 70% by weight with respect to the entire polymerizable layer. Is.

[Hydrophilic Binder Polymer] As the binder used in the photosensitive layer, overcoat layer or image formation promoting layer of the photosensitive material of the present invention, any binder can be used as long as the characteristics of the photosensitive layer are not significantly impaired. However, it is preferable to use a hydrophilic binder.

The hydrophilic binder is a binder having a hydrophilic group or / and a bond in the molecular structure.
Examples of hydrophilic groups include carboxyl groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonimide groups and amide groups. Examples of hydrophilic bonds include urethane bonds, ether bonds and amide bonds.

As the hydrophilic binder polymer, it is preferable to use a water-soluble polymer and / or a water-swellable polymer. The water-swellable polymer is a polymer that has an affinity for water but is not completely dissolved in water because the binder itself has a crosslinked structure and the like.

As the water-soluble or water-swellable binder, a natural or synthetic polymer compound can be used.
Examples of natural polymers include water-soluble polysaccharides (eg, starch derivatives, cellulose derivatives, alginic acid, pectic acid, gum arabic, pullulan, dextran) and proteins (eg, casein, gelatin).
These may be artificially modified if necessary. It can also be used after being modified or crosslinked during coating and drying. As the synthetic polymer, a polymer of a water-soluble monomer or a copolymer of this and another monomer can be used. Examples of the water-soluble monomer in this case include a monomer having a chemical structure such as a carboxyl group, an acid anhydride group, a hydroxyl group, a sulfonic acid (salt) group, an amide group, an amino group, and an ether group. Regarding such monomers, "Applications and Markets of Water-soluble Polymers" (CMC 16-1
See page 8). Copolymers obtained by polymerizing these monomers or crosslinking polymers obtained by copolymerizing these monomers with other monomers can also be used (for example,
Copolymers described in U.S. Pat. No. 4,913,998).

As other synthetic polymers, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide and derivatives or modified products thereof can be used.

For example, in the case of polyvinyl alcohol,
Various saponification degrees can be used. Further, copolymer modified polyvinyl alcohol can also be used. The copolymerization modification is a method in which a copolymer of vinyl acetate and another monomer is saponified to obtain modified polyvinyl alcohol. As the monomer to be copolymerized, any monomer can be used as long as it is copolymerized with vinyl acetate. Examples of copolymerizable monomers include ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, methyl methacrylate and acrylamide.

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 modified by a polymer reaction. Specifically, the hydroxyl group is etherified,
Modifications such as esterification and acetalization. Furthermore, it is also possible to use crosslinked polyvinyl alcohol. In this case, polyvinyl alcohol is cross-linked using 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) as a cross-linking agent. For these modified polyvinyl alcohols and cross-linked polyvinyl alcohols, refer to “Poval” No. 3
Eds., Polymer Society (pp. 281-285 and 256-260).

The molecular weight of these hydrophilic polymers is 30.
The range of 00 to 500,000 is preferable. The application amount is 0.05-
20 g / m ^2, more preferably, 0.1 to 10 g / m ²
Is the range.

In the case of development in which the surface of the light-sensitive material is overheated while being exposed to the air, oxygen penetrating the polymerizable layer inhibits radical polymerization or crosslinking. Therefore, each layer preferably has a function of preventing the influence of oxygen in the air on the polymerizable layer. For this function, the hydrophilic binder must be a substance with low oxygen permeability, and the oxygen permeability coefficient is 1.0 × 10 ^-11 cc.
· Cm / cm ² · it is preferable sec · cm · Hg or less.

As the polymer having a low oxygen transmission rate, a polyvinyl alcohol polymer, a copolymer of gelatin and vinylidene chloride is preferable. Here, the polyvinyl alcohol-based polymer means polyvinyl alcohol and modified polyvinyl alcohol (for example, saponified block copolymer of polyvinyl acetate and another monomer). The molecular weight is not particularly limited, but is preferably in the range of about 3000 to 500,000.

As the polymer having a low oxygen permeability, polyvinyl alcohol having a saponification degree of 50% or more, more preferably 80% or more, still more preferably 95% or more is particularly preferable.

[Base or Base Precursor] The light-sensitive material used in the present invention preferably contains a base or a base precursor.

As the bases and base precursors, 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 disclosed in JP-A-62-209448.
It is described in the official gazette. Examples of organic bases include tertiary amine compounds (described in JP-A-62-170954),
Bis, tris or tetraamidine compounds (described in JP-A-63-316760) and bis, tris or tetraguanidine compounds (JP-A-64)
No. -68746). 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 preferred base precursors include:
Salts of organic acids and bases that are decarboxylated by heating (JP-A-63-3)
16760, 64-68746, 59-180
No. 537 and 61-313431) and a urea compound that releases a base upon heating (JP-A-63-63).
-96159 gazette). 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) In addition, a basic metal compound that is poorly soluble in water and a compound that can undergo a complex formation reaction with a metal ion that composes the basic metal compound in water as a medium are contained between these two compounds in the presence of water. Method for releasing a base by the reaction of
No. 82).

The base precursor of the present invention is 50
It is preferably one that releases a base at a temperature of from 200 to 200 ° C, and more preferably one that releases a base at from 80 to 160 ° C.

A light-sensitive material using a base or a base precursor is described in JP-A-62-264041. Further, for a light-sensitive material using a tertiary amine as a base, see JP-A-62-1170954, and for a light-sensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. JP-A-6
Japanese Laid-Open Patent Publication No. 2-209523 discloses a light-sensitive material using a guanidine derivative having a solubility of 0.1% or less.
JP-A-62-209448 describes the light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal in JP-A-70845.

Further, a light-sensitive material using an acetylide compound as a base precursor is disclosed in JP-A-63-24.
Japanese Patent Application Laid-Open No. 63-46446 discloses a photosensitive material containing a propiolic acid salt as a base precursor and further containing silver, copper, a silver compound or a copper compound as a catalyst for a base formation reaction. And a light-sensitive material containing the above silver, copper, a silver compound or a copper compound in a state of being isolated from each other, JP-A-63-81338.
Japanese Patent Application Laid-Open No. 63-97942 discloses a photosensitive material containing a ligand in the free state in addition to the above-mentioned propiolic acid salt and the above-mentioned silver, copper, silver compound or copper compound. With salt,
Regarding a light-sensitive material containing a heat-melting compound as a reaction accelerator for a base-forming reaction, JP-A-63-46447 discloses that a sulfonylacetate is used as a base precursor, and a heat-melting compound further accelerates the reaction of a base-forming reaction. Regarding the light-sensitive material contained as an agent, JP-A-63-4845
JP-A-63-96652 discloses a light-sensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base as a base precursor, and further includes a nucleophile as a decomposition accelerator for the compound. The light-sensitive materials are described in JP-A-63-173039.

Regarding a light-sensitive material using a bis or trisamidine salt of a decarboxylable carboxylic acid as a base precursor, Japanese Patent Laid-Open No. 9441/1989 describes a light-sensitive material using a bis or trisguanidine salt. Each of them is described in JP-A-64-68749.

The base and the base precursor may be used in combination. The base or base precursor is preferably used in the range of 0.5 to 50 mol, and more preferably 1 to 20 mol, per mol of silver halide.

[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, P2
1-63; "Plastics Additives Second Edition" (Pl
astics Additives, 2nd Edition) Hanser Publishers,
Chap.5 P251-296; "Thermoplastics Additives" Marcel Dekker In
c. Chap.9 P345-379; “Plastic Additives An Industrial Guide” (Plastics Addit
ives An Industrial Guide) Noyes Publications, Sect
ion-14 P333-485 ； "The Technology of Solvents and Plasticizers" (The Technolo
gy of Solvents and Plasticizers) John Wiley & Son
s Inc. Chap.15 P903-1027); "Industrial Plasticizers, Per"
gamon Press); "Plasticizer Technology Vol.1, Reinhold P"
ublishing Corp.); "Plasticization and Plasticizer Process" (Plusticizati
on and Plusticizer Process, American Chemistry) can be used.

Compounds which can be melted in the layer by heating include US Pat. Nos. 3,347,675 and 3667.
No. 959, a polar substance; Research Disclosure, December 1976, pages 26-28, 1,10-decanediol, methyl anisate, biphenyl suberate; JP-A-62-151841. Sulfonamide derivatives, polyethylene glycol derivatives and cyclic amide compounds described in JP-A Nos. 62-151843 and 62-183450; JP-A-63-243
No. 835 and No. 63-253934, heat-meltable compounds; JP-B-59-25674 and JP-A-59-59674.
-101392, 60-82382 and 62.
-25085 compounds having an aromatic ring described in JP-A Nos. 61-283592, 63-15784, 64-1583, 57-146688, and 58-58;
104793, 58-205795, 62-1
42686, 62-144990 and 62-
Compounds having an ester or amide group described in JP-A No. 132675; JP-A Nos. 58-57989 and 58-
72499, 58-87094, 60-295.
No. 87, No. 60-56588, No. 60-123581.
No. 60, No. 60-16888, No. 61-242884,
Compounds having an ether or thioether structure described in JP-A Nos. 61-31287, 61-27285 and 61-31287;
No. 61-112689 and No. 61-116584.
No. 61-151478 and No. 62-26718.
No. 6, ketones, carbonates, sulfoxides, phosphate compounds; and JP-A-59-159.
393, 63-15783 and 63-249.
Compounds having a phenolic hydroxyl group described in JP-A No. 686 can also be used.

Preferred heat development accelerators are glycols (eg, diethylene glycol, dipolypropylene glycol), polyhydric alcohols (eg, glycerin, butanediol, hexanediol), sugars, formate esters, ureas (eg, urea). , Diethylurea, ethyleneurea,
Propylene urea), urea resin, phenol resin, amide compound (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 amount of the thermal development accelerator added is arbitrary as long as the characteristics of the light-sensitive material are not significantly impaired, but it is preferably 0 to ² g / m ^{2 and} more preferably 0 to 1 g / m ² .

[Colorant] In the present invention, 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 coloring agent for this purpose, any known coloring agent 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 significantly hinders the photosensitivity and developability of the silver halide. It is possible to use. When the colorant is used for the purpose of preventing halation or coloring the image, it is preferably added to the polymerizable layer. Also,
When 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 pigment that can be used as the colorant, commercially available pigments and color indexes (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), "Latest pigment application technology" (CMC Publishing,
1986, "Printing Ink Technology" (CMC Publishing, 1
The pigments described in pp. 984) can be used.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. 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, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, etc. can be used.

These pigments may be used without being surface-treated, or may be used after being surface-treated. Surface treatment methods include resin or wax surface coating, surfactant attachment, and reactive substances (eg, silane coupling agents, epoxy compounds, polyisocyanates, etc.)
It is possible to consider a method of binding the pigment to the surface of the pigment. The above surface treatment method is "property and application of metal soap" (Koushobo),
"Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 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, an ultrasonic disperser,
A sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a desperser, 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. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, and methine dyes.

Dyes for preventing irradiation which have little influence on the sensitivity of silver halide are described in JP-B-41-20389.
No. 43-3504, No. 43-13168, and JP-A No. 2-39042, and US Pat. No. 36.
No. 97037, No. 3423207, No. 28657.
52, British Patent Nos. 1030392 and 110
Nos. 0546 can be mentioned as examples.

The content of the colorant is not particularly limited as long as it does not significantly hinder the polymerization reaction of the polymerizable layer or the light sensitivity and developability of the silver halide. In addition, the appropriate addition amount changes depending on which layer contains the pigment, the pigment or the dye is used. Also, since the appropriate addition amount changes depending on the absorbance of the colorant,
Although it is difficult to unconditionally specify the optimum addition amount,
01 to ² g / m ² , more preferably 0.05 to 1 g / m
^{Is 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 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 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. The development terminator may be added to the layer at any time.

[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.

[Mat Agent] Examples of the mat agent that can be contained in the overcoat layer or the image formation promoting layer provided on the uppermost layer of the light-sensitive material are various polymer powders (eg, natural products such as starch, polyethylene). And other synthetic polymers). The particle size is preferably in the range of about 1 to 50 μm.

[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 Al salt, N-nitrosodiphenylamine,
Allyl thiourea, aryl phosphite, p-toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-
Butyl catechol, phenothiazine, chloranil, p
Mention may be made of methoxyphenol, pyrogallol, hydroquinone, and alkyl- or aryl-substituted hydroquinones.

[Image Forming Method] Image formation by thermal development is performed as follows. That is, when a latent image is formed on a photosensitive layer containing silver halide by imagewise exposure and then (or simultaneously) the photosensitive layer is uniformly heated (heat-developed) to develop the silver halide on which the latent image is formed. At the same time, the polymerizable compound in that portion (or in the portion where the latent image is not formed) is polymerized and cured to form a polymerized image.

Image exposure is carried out using a light source which 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 of the light-sensitive material of the present invention is carried out by a dry method (heat development) by heating. 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 opening the surface in air and heating
Since oxygen in the air may permeate into the light-sensitive material to inhibit the polymerization reaction, it is preferable to use the above-mentioned binder polymer having a low oxygen transmission rate in at least a part of the layer of the light-sensitive material. The heating temperature is 60 to 200 ° C., more preferably 100 to 150 ° C., and the heating time is 1 to 180 seconds, more preferably 5 to 60 seconds.

After thermal development, the image obtained has a chemical property and a physical property (for example, solubility, surface tackiness, adhesion strength with a support, softening point) between the cured part and the uncured part. , Refractivity, dielectric constant, diffusivity, and colorability) are used for post-treatment.

Examples of the post-processing include the following processing. 1. By utilizing the difference in solubility between the uncured portion and the cured portion, only the uncured portion is eluted to form a polymer image. 2. The uncured portion or the cured portion is selectively transferred to another sheet by utilizing the difference in the adhesive strength between the uncured portion and the support of the cured portion. 3. By utilizing the difference in surface tackiness between the uncured portion and the cured portion, a coloring substance (toner) is attached to the uncured portion to visualize the image. 4. The image is visualized by selectively dyeing the uncured portion or the cured portion. Also, these can be used in combination. For these image forming methods, see Japanese Patent Application No. 2-332626.
No. 0, No. 3-131788, No. 3-131789,
No. 3-131790 and No. 3-131791 specification.

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

When the uncured portion is eluted to form a polymer image, after thermal development, it is immersed in a liquid (etching solution) capable of removing the uncured portion of the polymerizable layer. As the etching liquid, a liquid that dissolves or swells the uncured polymerizable layer, such as an organic solvent, an alkaline aqueous solution, or a mixed solution thereof, is used. As the alkaline compound, potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium metasilicate, sodium metasilicate, potassium phosphate, sodium phosphate, ammonia, monoethanolamine, diethanolamine, triethanolamine, etc. The amino alcohols can be mentioned. Various organic solvents may be added to the water-based etching solution, if necessary. Examples of the organic solvent include lower alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and phenethyl alcohol, aromatic alcohols, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and the amino alcohols described above as bases. Etc. 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. .

The present invention is described in more detail below by referring to Examples, but the present invention is not limited thereto.

[0128]

【Example】

[Example 1] "Preparation of aluminum support" A surface of an aluminum plate having a thickness of 0.30 mm was covered with a nylon brush and a pumice stone (4
(00 mesh) in water suspension, and then thoroughly washed with water. 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. It was neutralized and washed with a 20% nitric acid aqueous solution, and then washed with water. The obtained aluminum plate was subjected to an alternating sine 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 160 coulomb / dm ² ). Then, electrolytic graining treatment was performed in a 1% nitric acid aqueous solution. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Following this treatment, it was desmutted in a 30% aqueous sulfuric acid solution at 55 ° C. for 2 minutes. Next, ² so that the thickness becomes 2.7 g / dm 2.
Anodizing treatment was performed in 0% sulfuric acid aqueous solution (current density 2
A / dm ² ). The obtained aluminum plate was immersed in a 3 wt% sodium silicate aqueous solution at 70 ° C. for 20 seconds, washed with water, and dried.

[Formation of Polymerizable Layer] The following coating liquid was applied onto the 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 liquid 13.0 g Methyl ethyl ketone 74.0 g ───────────────────── ────────────────

(Pigment Dispersion Liquid) ──────────────────────────────────── Pigment Dispersion Liquid ─── ───────────────────────────────── Chromophtal red A2B 18g benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 12 g cyclohexane 30 g propylene glycol monomethyl ether 40 g ─────────────────────────────────────

[Formation of Photosensitive Layer] (Preparation of Silver Halide Emulsion) 16 g of gelatin and 0.5 g of sodium chloride were dissolved in 1500 ml of water, and the pH was adjusted to 3.2 with 1N sulfuric acid. The resulting gelatin solution is 5
The temperature was kept at 0 ° C. To this solution, 300 ml of an aqueous solution containing 71 g of potassium bromide and 300 ml of an aqueous solution containing 0.59 mol of silver nitrate were simultaneously added at the same flow rate over 50 minutes. One minute after this was completed, 200 m of an aqueous solution further containing 4.3 g of potassium iodide
1 was added at a constant flow rate over 5 minutes. To the resulting emulsion, 1.2 g of poly (isobutylene-co-maleate monosodium) was added and allowed to settle, washed with water to desalt, and then 24 g of gelatin was added and dissolved, and further 5 mg of sodium thiosulfate and the following additions were added. Sensitizing dye (Dye-1)
0.5g was added and chemical sensitization was performed at 60 ° C for 15 minutes.
1000 g of silver halide emulsion was prepared.

(Sensitizing dye)

[Chemical 16]

(Preparation of Base Precursor Dispersion) 250 g of powder of the following base precursor (BP-1) was used in a Dynomill disperser and 750 g of a 3% by weight aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.). Dispersed in. The particle size of the base precursor is about 0.5
It was less than μm.

(Base precursor)

[Chemical 17]

(Formation of Photosensitive Layer) A coating solution having the following components was prepared, and the obtained solution was applied onto the polymerizable layer and dried to form a photosensitive film having a dry film thickness of about 1.2 μm. The property layer was provided.

──────────────────────────────────── Coating solution for the photosensitive layer ───── ─────────────────────────────── Polyvinyl alcohol with a saponification degree of 81.5% (trade name: PVA-405, Kuraray 10 wt% aqueous solution of Co., Ltd. 42.0 g The above base precursor dispersion 12.5 g Reducing agent (compound (A)) 0.9 g Propionamide (heat development accelerator) 2.0 g The following additives (AD -1) 0.13 wt% methanol solution 5.4 g 0.13 wt% methanol solution of the following additive (AD-2) 5.4 g The above silver halide emulsion 3.7 g Surfactant (SA-1 ) 5 wt% aqueous solution 9.0 g water 106.0 g ───────────────────────── ──────────

[0138]

[Chemical 18]

[0139]

[Chemical 19]

[0140]

[Chemical 20]

"Formation of overcoat layer" Saponification degree 9
8.5% polyvinyl alcohol (trade name: PVA-1
17, a 10 wt% aqueous solution of Kuraray Co., Ltd. and 4 g of a 5 wt% aqueous solution of the above-mentioned surfactant (SA-1) were mixed,
A coating liquid was prepared. The obtained liquid was applied onto the photosensitive layer and dried to form an overcoat layer having a dry film thickness of about 3.0 μm.

(Image Forming Method and Evaluation) An original film was brought into close contact with the light-sensitive material obtained as described above, and 5
Using a 00W tungsten lamp, exposure was carried out for 1 second through a bandpass filter which transmits light of 500 nm. Next, the aluminum support surface of the light-sensitive material was brought into close contact with a hot plate heated to 135 ° C., and the overcoat layer was heat-developed for 30 seconds while exposing the surface to air. A silver image was observed in the exposed portion. It was Next, add this to Fuji PS Developer DN-3.
After immersing in C (manufactured by Fuji Photo Film Co., Ltd.) at room temperature for 1 minute to perform etching, it was thoroughly washed with water to elute and remove the photosensitive layer in the unexposed area. As a result, the exposed area was colored with a red polymer. Relief image was formed. When the printing plate thus obtained was mounted on a Heidel KOR-D printing machine and printed, a good printed matter was obtained. In addition, even after storing this photosensitive material at room temperature for 6 months,
It gave an image with good contrast.

[Example 2] (Preparation of silver halide emulsion) Phthalated gelatin (protective colloid; phthalation rate 95%), potassium bromide and water were placed in an appropriate amount in a container heated to 55 ° C. After adding ammonium, while maintaining the pAg value in the reaction vessel at 7.60, the silver nitrate aqueous solution and the molar ratio of iridium to silver are 5 × 1.
Hexachloroiridium (III) so that it becomes 0 ^-7 mol
Monodisperse silver iodobromide emulsion grains having an average grain size of 0.25 μm are prepared by adding potassium bromide and an aqueous solution containing potassium iodide to which acid salts have been added by the double jet method, and then adding potassium iodide. A silver iodide content of 2 mol%) was prepared. In these emulsion grains, 98% of the total number of grains were present within ± 40% of the average grain size. After the emulsion was desalted, the pH was adjusted to 6.2 and the pAg was adjusted to 8.6, and then gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid, and then the above spectral sensitizing dye (Dye -1) in 2 mol / l methanol solution 200 cc / kg emulsion
After addition, the mixture was stirred and held at 60 ° C. for 15 minutes to obtain a silver halide emulsion. The content of phthalated gelatin was 0.05 g per 1 g of silver halide emulsion, the content of silver halide was 0.15 g in terms of metallic silver, and the grain size of silver halide was about 0.3 μm.

(Formation of Photosensitive Layer) In the same manner as in Example 1, a polymerizable layer was formed on the support. Next, prepare a coating liquid of the following components, apply the obtained liquid on the polymerizable layer,
After drying, a photosensitive layer having a dry film thickness of about 3.5 μm was provided.

──────────────────────────────────── Coating solution for the photosensitive layer ───── ─────────────────────────────── Polyvinyl alcohol with a saponification degree of 98.5% (trade name: PVA-110, Kuraray 10 wt% aqueous solution of Co., Ltd. 20.0 g The above base precursor dispersion 1.25 g Reducing agent (compound (A)) 0.45 g Sorbitol (heat development accelerator) 0.4 g The following additives (AD- 3) 0.11% by weight methanol solution 0.83 g The above silver halide emulsion 0.5 g 5% by weight aqueous solution of the following surfactant (SA-2) 0.4 g water 3.0 g ────── ──────────────────────────────

(Additive)

[Chemical 21]

(Surfactant)

[Chemical formula 22]

(Image Forming Method and Evaluation) Using the photosensitive material obtained as described above, an image was formed and evaluated in the same manner as in Example 1. As a result, good images and printed matter were obtained.

Example 2 100 g of trimethylolpropane triallyacrylate (polymerizable compound), 0.4 g of the following copolymer (a), 0.02 g of the following mercapto compound (a), the following compound (x) and An oily solution was prepared by uniformly dissolving 20 g of methylene chloride. To 100 g of this oily solution, 14 g of the silver halide emulsion prepared in Example 1 and 3.4 g of compound (A) were added, and the mixture was homogenized at 1300 rpm. p. m. The silver halide emulsion was emulsified in an oil solution by stirring for 5 minutes.

[0150]

[Chemical formula 23]

[0151]

[Chemical formula 24]

[0152]

[Chemical 25]

5 g of the obtained emulsion was mixed with 30 g of a solution of 4 g of the following copolymer (b) (binder polymer) in 30 g of propylene glycol monomethyl ether, and the base precursor aqueous dispersion used in Example 1 was mixed therewith. Add 8 g of liquid and 0.5 g of phthalocyanine,
With a homogenizer, 1300 r. p. m. And stirred for 5 minutes to emulsify to prepare a photosensitive composition.

[0154]

[Chemical formula 26]

This photosensitive composition was applied onto the aluminum support used in Example 1 and dried to form a photosensitive layer having a dry film thickness of about 4 μm. A 10% aqueous solution of polyvinyl alcohol was applied onto this layer so that the dry film thickness was about 4 μm, and dried to prepare a light-sensitive material.

An original film was brought into close contact with the light-sensitive material obtained as described above, and was exposed for 1 second at an illuminance of 500 lux using a 500 W tungsten lamp. Next, the aluminum support surface of the light-sensitive material was brought into close contact with a hot plate heated to 140 ° C., and the polyvinyl alcohol layer was heat-developed for 20 seconds while exposing the surface to the air, and a silver image was observed in the exposed portion. It was Then, add this to water at 40 ° C for 3
After washing with water for 0 seconds to dissolve and remove the polyvinyl alcohol layer, it was immersed in methanol for 1 minute to elute and remove the photosensitive layer in the unexposed area, and a relief image of the polymer was formed in the exposed area. When the printing plate thus obtained was mounted on a Heidel KOR-D printing machine and printed, a good printed matter was obtained. Also, this light-sensitive material is 6 at room temperature.
Even after storage for a month, it gave images with good contrast.

Claims (2)

[Claims] 1. A photothermographic material comprising a support and a photosensitive polymerizable layer containing a silver halide, a reducing agent and a polymerizable compound, wherein the reducing agent is 0.1% by weight with respect to water. %
A heat-developable photosensitive material characterized by being a substance which dissolves as described above. 2. The photothermographic material according to claim 1, wherein the reducing agent is a compound represented by the following formula (1). [Chemical 1] In the formula (1), R ¹ represents an optionally substituted alkyl group, aryl group or heterocyclic group, and R ² represents an optionally substituted alkylene group, arylene group or divalent heterocyclic group. , X represents a hydrophilic group.