JPH0545025B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a method for recording photographic images, and more particularly to a method for forming a polymer image by causing a polymerization reaction in a dry process using silver halide as a trigger. "Prior art" The technology of forming polymer images through photopolymerization reaction using organic dyes as photosensitizers (photopolymerization initiators) is well known, but its sensitivity is usually ISO10 ^-3 .
and is significantly inferior to silver halide photographic materials. Using silver halide as a trigger,
Various methods have been attempted to initiate a polymerization reaction by taking advantage of the high rate of broadening in the development process. for example,
Special Publications No. 45-11149, No. 45-30338, No. 46-6581, No.
46-21723, 47-12638, 47-14667, 47-
14668, 47-14669, 47-18585, 47-
20741, 49-1569, 49-1570, 49-10697, JP-A-57-138632, 57-142638, 57-
176033, 58-107529, 58-169143, 58-
As described in Japanese Patent Publication No. 174947 and Japanese Patent Publication No. 46-16357, a method in which a polymerization reaction is caused by radicals generated in a reducing agent oxidized during the development process of silver halide, Japanese Patent Publication No. 41-18862. As described in the publication, Japanese Patent Publication No. 39-2657 describes a method in which a redox reaction between a silver image obtained by developing silver halide and a peroxide causes a polymerization reaction using radicals generated from the peroxide. As described, after silver halide development, silver ions remaining in unexposed areas are dissolved, and a redox reaction between this and peroxide causes a polymerization reaction with radicals generated from the peroxide, a US patent. As described in No. 3029145, silver halide is developed with iron () salt, and the radicals generated from the peroxide undergo a polymerization reaction through a redox reaction between the iron () salt remaining in the unexposed area and the peroxide. , and furthermore, JP-A-55-
As described in Japanese Patent No. 149939, there is a method in which a polymerization reaction is directly caused by a reducing agent remaining in an unexposed area after silver halide is developed. These methods utilize either the raw materials (silver halide, reducing agent) or products (silver image, oxidation product of the reducing agent) involved in the silver halide development process to generate radicals either directly or through a subsequent reaction. It is something that generates. It is estimated that polymer images can be formed with a sensitivity close to that of silver halide, but all require subtractive processing in the development of silver halide and the process of generating radicals and polymerizing, and they also require the use of peroxides. The method used has the disadvantage that the recording material deteriorates and fog is generated due to dark polymerization caused by radicals generated by its decomposition. Another disadvantage is that the polymerization reaction generally takes a long time. "Problems to be Solved by the Invention" The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, especially the wet processing, to form a polymer image with only a short heating time, and to use only a small amount of silver halide. The object of the present invention is to provide a new image recording method capable of recording polymer images with a photosensitivity comparable to that of ordinary silver halide photographic materials. ``Means for Solving the Problems'' The present inventor has developed a polymer image by heating it for an extremely short period of time after image exposure using the method described below.
The present invention was achieved by discovering that it is possible to record with a photosensitivity comparable to that of silver halide photographic materials. That is, the present invention involves image-exposure of a photosensitive material containing a photosensitive silver halide, a polymerizable vinyl monomer, a thermal polymerization initiator, and a reducing agent represented by the following general formula (), and then uniformly heated. , is an image recording method characterized by forming a polymer image on unexposed areas. General formula () In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Represents a group selected from an alkyl group and a substituted alkyl group, and Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, and a halogen atom. represents a group. The substitution position of the hydroxyl group on the benzene ring may be any of the ortho, meta and para positions. "Function" The photosensitive material used in the present invention basically has a photosensitive layer consisting of a photosensitive silver halide, a polymerizable vinyl monomer, a thermal polymerization initiator, a reducing agent represented by the general formula (), and generally a binder polymer. It is provided on a support. The photosensitive layer may consist of a single layer, or it may consist of two or more adjacent layers, each layer having any of the above-mentioned components. Therefore, it is possible to provide a photosensitive silver halide-containing layer and a polymerizable vinyl monomer-containing layer, and contain a thermal polymerization initiator and a reducing agent in either layer, respectively. A layer containing an agent can also be provided. A single layer is preferred from a manufacturing cost standpoint. The photosensitive layer can further contain an organic silver salt oxidizing agent, a base or base precursor, and a thermal solvent as described below, for the purpose of increasing the efficiency of the polymerization reaction. Furthermore, as will be described below, if it is necessary to visualize the resulting polymer image, the photosensitive layer can contain materials necessary for that purpose. Although the mechanism of image formation by the method of the present invention is not clear, it is possible to form a positive polymer image from a positive original by heating for a very short time after image exposure, and only by using a small amount of silver halide. It is possible to record polymer images with a light sensitivity comparable to that of ordinary silver halide photographic materials. The present invention will be explained in more detail. As the photosensitive silver halide used in the present invention,
Silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, silver iodide, and other materials made by known methods are used. The grain size of silver halide ranges from 0.001 μm to 2 μm. Silver halide can be chemically sensitized using a chemical sensitizer such as sulfur, selenium, tellurium, gold, platinum, palladium, rhodium, or iridium, or a reducing agent such as silver halide. Dye sensitization may also be carried out by a known method. For more information on these methods, see
“The Theory of the Photographic Process” by Mees, James.
of the Photographic Process” (The
It is described in books such as Mecmillan Co. (1966)). The dye sensitization described above is useful for increasing the sensitivity of photosensitive silver halide and selecting the sensitive wavelength range. The dyes used include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are
It is a pigment belonging to cyanine pigments, merocyanine pigments, and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat.
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. In the present invention, an organic silver salt oxidizing agent can be used in addition to the photosensitive silver halide for the purpose of oxidizing the reducing agent during heating in the latent image forming region. this is,
Although it is a silver salt that is relatively stable against light, when it is heated in the presence of silver halide that has a latent image, it oxidizes the reducing agent and is itself reduced to silver. To name a few, fatty acids (behenic acid, stearic acid, lauric acid, maleic acid, adipic acid, etc.)
compounds having a mercapto group or a thione group (3-mercapto-4-
phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, etc.), compounds having an imino group (benzotriazole and its derivatives described in Japanese Patent Publication Nos. 44-30270 and 45-18416, etc.) Silver salts such as The polymerizable vinyl monomer used in the present invention is a compound having at least one vinyl group or vinylidene group and capable of radical polymerization, including known acrylic acid and methacrylic acid esters, acrylic acid metal salts (e.g. , barium acrylate,
calcium acrylate), acrylamide, N,
N-methylenebisacrylamide, vinyl ethers, N-vinyl compounds (for example, N-vinylcarbazole), vinyl acetate, and the like are used.
Among these, esters of acrylic acid and methacrylic acid are particularly suitable for the present invention. Specific examples thereof are shown below using acrylic esters. (Specific examples of compounds in which one or all of these acryloyl groups are substituted with methacryloyl groups, that is, mixed esters of acrylic acid and methacrylic acid and methacrylic esters are omitted, but they are applicable to the present invention as well as acrylic esters. ) For example, monoacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate;
Diacrylates such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate; trimethylolpropane triacrylate, pentaerythritol triacrylate,
Tri- and tetraacrylates such as pentaerythritol tetraacrylate; and the following polymerizable prepolymers, such as Japanese Patent Publication No. 52-7361
Polybasic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, adipic acid, etc.) and polyhydric alcohols (e.g., ethylene glycol, Polyester acrylate (or oligoester acrylate), polyurethane acrylate obtained by the reaction of an acrylic ester having a hydroxyl group with isocyanates, and epoxy acrylate as described in Japanese Patent Publication No. 48-41708. In addition, in the present invention, two or more types of monomers can also be used in combination. The thermal polymerization initiator used in the present invention is generally a compound that thermally decomposes under heating to generate polymerization initiating species (particularly radicals), and those commonly used as radical polymerization initiators are suitable for the present invention. used. For example, "Addition Polymerization/Ring-Opening Polymerization" edited by the Editorial Committee of Polymer Experiments, Japan Society of Polymer Science (1983, Kyoritsu Publishing)
Some specific examples include azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, benzoyl peroxide, di-t −
Examples include organic peroxides such as butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide, and inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate. These can be used alone as thermal polymerization initiators, but redox initiators that generate radicals through a two-component redox reaction can also be used. For example, the above inorganic or organic peroxide and iron () salt, sulfite, Examples include combinations with reducing agents such as sodium hydrogen and dimethylaniline. Note that if the monomer itself has a high polymerizability and can initiate polymerization simply by heating, there is no particular need to use a thermal polymerization initiator. The reducing agent used in the present invention has the general formula ()
Aminophenol and its derivatives are represented by the following substituents: The alkyl group and the alkyl moiety of the substituted alkyl group may be linear or branched, and have 1 to 18 carbon atoms, more preferably 1 to 5 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
Examples include tert-butyl group, n-amyl group, tert-amyl group, etc. Substituents for alkyl groups include hydroxyl group, chlorine and bromine atoms, carbon atoms 1 to 18,
More preferably 1 to 5 alkoxy groups, phenyl groups, substituted phenyl groups (substituents include chlorine and bromine atoms, alkyl groups or alkoxy groups having 1 to 5 carbon atoms, and the positions are o, m, and p). any), number of carbon atoms is 1 to 18, more preferably 1 to 18
Examples include the acyl group of No. 5. The alkoxy group is
It has an alkyl chain having 1 to 18 carbon atoms, more preferably 1 to 5 carbon atoms. As an aryl group,
Phenyl group and substituted phenyl group (substituents include chlorine and bromine atoms, alkyl groups or alkoxy groups having 1 to 5 carbon atoms, and the positions are o, m,
p). Furthermore, examples of the halogen atom include chlorine, bromine, fluorine, and iodine atoms. Specific examples of preferred reducing agents include p-aminophenol, m-aminophenol, o-aminophenol, 2,6-dichloro-p-aminophenol, 2,6-dibromo-p-aminophenol, 2,6 -dimethyl-p-aminophenol, 3,5-dimethyl-p-aminophenol,
2-phenyl-p-aminophenol, 2-chloro-p-aminophenol, 2,6-dimethoxy-p-aminophenol, 2,3,6-trimethyl-p-aminophenol, 2,3,5-trimethyl- p-aminophenol, 3,6-dimethyl-p-aminophenol, 3-methoxy-p-aminophenol, 3,5-dimethoxy-p-aminophenol, 4-chloro-5-methyl-o-aminophenol, etc. be. Among these aminophenol derivatives, p-aminophenol and its substituted derivatives are particularly preferred. Note that two or more types of reducing agents can be used in combination. Binder polymers include water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, gum arabic, casein, methyl cellulose, and polymethyl methacrylate, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride- Acrylonitrile copolymer, polyvinyl acetate, vinyl acetate-vinyl chloride copolymer, styrene-acrylonitrile copolymer, polyester, ABS resin, polyamide, chlorinated polyethylene, chlorinated polypropylene, polyvinyl butyral, polyvinyl formal, acetyl cellulose, etc., which are soluble in organic solvents. Polymers and the like are used. Solvents used to dissolve and apply these polymers include water, acetone, toluene, methylene chloride, methylene dichloride, chloroform, methyl ethyl ketone, ethyl acetate, methyl acetate, dimethylformamide, dimethyl sulfoxide, and the like. Two or more binder polymers can be used in combination. For example, silver halide can be prepared as a gelatin emulsion, and this can be added to a coating solution consisting of a binder other than gelatin, a monomer, etc., and then applied. In this case, the two or more binders do not necessarily need to be mixed uniformly. Furthermore, the monomers do not necessarily need to be uniformly mixed with the binder. For example, a water-insoluble monomer may be emulsified or microencapsulated in an aqueous solution of a water-soluble binder polymer to be heterogeneously dispersed. The photosensitive layer may contain a base or a base precursor for the purpose of accelerating the development of silver halide and thus the polymerization reaction. Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates; ammonium water; Oxides; hydroxides of quaternary alkylammonium; hydroxides of other metals, etc., and organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines (e.g., triethanolamine, diethanolamine, monoethanolamine, triethylenediamine)), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamino)phenyl]methane) ), heterocyclic amines, amidines, hydrazine derivatives (e.g., benzoyl hydrazide, malonyl dihydrazide, phenyl hydrazide, p-tolyl hydrazide, phthal dihydrazide), cyclic amidines, guanidines, and cyclic guanidines. pKa is 8
The above are preferred. When a base is included in a light-sensitive material, it is preferably added in the form of a precursor. Examples of base precursors include salts of organic acids and bases that decompose by decarboxylation upon heating, compounds that decompose to release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothsen rearrangement, and Beckman rearrangement. Those that cause a reaction and release a base are preferably used. Preferred base precursors include:
Salts of trichloroacetic acid described in British Patent No. 998949, salts of α-sulfonylacetic acid described in U.S. Patent No. 4060420, salts of propiolic acids described in Japanese Patent Application No. 58-55700, and salts of propiolic acids described in U.S. Patent No. 4088496. The 2-carboxycarboxamide derivative described above, a salt with a thermally decomposable acid using an alkali metal or alkaline earth metal in addition to an organic base as the base component (JP-A-59-195237
No.), JP-A-59-168440 using Lothsen rearrangement
and aldoxime carbamates described in JP-A-59-157637, which produce nitriles upon heating. Other British Patent No. 998945, US Patent No.
No. 3220846, Japanese Patent Application Publication No. 50-22625, British Patent No.
The base precursors described in No. 2079480 and the like are also useful. Specific examples of base precursors particularly useful in the present invention are shown below. Guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, p-chlorophenylsulfonylacetate guanidine, p-methanesulfonylphenylsulfonylacetate guanidine, potassium phenylpropiolate, cesium phenylpropiolate , guanidine phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine 2,4-dichlorophenylpropiolate, diguanidine p-phenylene-bis-propiolate, tetramethylammonium phenylsulfonylacetate, phenylpropiolate Tetramethylammonium olate. These base precursors can be used alone or in combination. The photosensitive layer can further contain, and is generally preferred, a thermal solvent for the purpose of promoting thermal development and polymerization reactions of the silver halide and organic silver salt oxidizing agent. The heat solvent is at the temperature of heat development, e.g.
It has a melting point in the range of °C to 200 °C, dissolves the hydrazine derivative in a molten state, or softens the photosensitive layer,
It is a substance that has the function of promoting its movement, and is difficult to react with silver salts, monomers, hydrazine derivatives, etc. A very wide range of organic or inorganic compounds can be selected, specific examples being sorbitol, pentaerythritol, trimethylolpropane, trimethylolethane, hexanediol, cyclohexanediol, polyhydroxy compounds such as saponin, urea, dimethylurea, etc. , acetamide, N-methylacetamide, and the like. In addition, known preservatives, antifoggants, etc. can be added to the photosensitive layer, and an antihalation layer, an antistatic layer, a protective layer, etc. can be provided. As the support, paper, resin-coated paper, film such as polyethylene terephthalate or triacetyl cellulose, aluminum plate, etc. can be selected and used depending on the purpose of use. The amounts of the components constituting the above solid photosensitive layer are as follows. Polymerizable vinyl monomer is approximately 0.1 to 3000g/m ²
(For example, approximately 0.1 to 30g/approx. for use in planographic printing plates.
m ² , approximately 0.6 to 3000 g/m ² for letterpress printing plate applications)
Used within the range of In addition, photosensitive silver halide is 0.001 to 0.5 per gram of polymerizable vinyl monomer.
g, more preferably 0.005 to 0.1 g, and the organic silver salt oxidizing agent is 0 to 20 g per mole of silver halide.
mol, more preferably 0 to 5 mol, and the reducing agent of the present invention is 0.1 to 20 mol per mol of total silver salt,
More preferably, it is 0.5 to 5 mol, and the binder polymer is 0 to 10 g, more preferably 0 to 2 g.
and the base or base precursor is 0 to 3 g,
More preferably, it is 0 to 1 g, and the hot solvent is 0 to 3 g.
g, more preferably 0 to 1 g. The dry film thickness of the photosensitive layer can vary widely depending on the intended use of the recording material. For example, for ordinary image recording purposes and uses such as lithographic printing plates, it is 0.1 to 50 μm, more preferably 0.5 to 10 μm, but for letterpress printing plates and applications using relief itself, it is 1 μm to 5 μm.
m, more preferably 0.1 to 3 μm. If the development and/or polymerization reaction of silver salt is inhibited by oxygen in the air, use a substance with low oxygen permeability on the surface of the photosensitive layer (for example, polyvinyl alcohol, gelatin, or vinylidene chloride and vinyl chloride). , a copolymer with acrylonitrile, etc.) is preferably provided. The thickness of the oxygen prevention layer is 0 to 20 μm, more preferably 0 to 20 μm.
It is 5 μm. Note that when this layer is provided, it can also serve as a protective layer. Image recording according to the present invention is carried out by exposing the above-mentioned image recording material to light and then uniformly heating it, and it is possible to form the polymer in the form of an image with just this operation. Image exposure is performed using a light source containing a wavelength to which photosensitive silver halides (including dye-sensitized ones) are sensitive, such as tungsten lamps, halogen lamps, mercury lamps, fluorescent lamps, xenon lamps, lasers,
This can be done using visible light or ultraviolet light using LEDs, CRTs, etc. Furthermore, image exposure may be performed using X-rays or electron beams. The exposure amount varies depending on the sensitivity of the silver halide, but is generally 10 ^-2 to 10 ³ ergs/
^cm2 . Heating can be performed with or without contact using a hot plate, heat roller, infrared lamp, oil bath high frequency heater, or the like.
Alternatively, it is also possible to incorporate a resistance heating element such as carbon black into the recording material and energize it to generate Joule heat and heat the recording material. Heating temperature is 80
The heating temperature is in the range of 1 to 200°C, more preferably 100 to 130°C, and the heating time is in the range of 1 to 300 seconds, more preferably 5 to 60 seconds. If oxygen in the air inhibits the polymerization reaction and/or development of the silver salt, a plastic film or the like can be placed in close contact with the photosensitive layer and heated. The image-formed polymer thus obtained can be visualized or developed by various methods depending on the purpose of use, and can be used as a final image.
For example, when used as a printing plate or relief, it can be developed with a solvent. The solvent used is one that does not dissolve the polymer image area but dissolves the uncured area. For example, when a water-soluble polymer such as polyvinyl alcohol is used as a binder, development can be performed with water.
In this case, if the photosensitive layer contains in advance a dye or pigment that does not desensitize silver halide or is difficult to desensitize, a visible image can be immediately obtained by solvent development. On the other hand, dry processing alone can convert polymer images into visible images. For example, the
As described in Japanese Patent No. 40537, by utilizing the difference in adhesiveness between the polymerized portion and the unpolymerized portion, each can be separated onto two sheets by peel development. (For visualization, as mentioned above,
A photosensitive layer can be selectively applied to only the colored layer in advance to form a visible image. Additionally, the polymer allows for controlled color development or dye bleaching reactions to convert the polymer image into a visible image. For example, as described in Japanese Patent Application Laid-Open No. 52-89915, a two-component thermosensitive coloring material is used, and the two components move and react under heating to produce an image. As described in JP-A-57-179836 and JP-A-57-197538, a two-component color-forming material is used as a microorganism containing a monomer. A method of separating the inside and outside of the capsule, polymerizing it, developing it under pressure, and destroying the uncured capsule to develop color.
241487, a method for controlling the bleaching of dyes (bleaching in uncured areas) using a polymer image as a barrier;
A method of bleaching the dye with an unpolymerized monomer as described in No. 59-222717 is used. When using these visualization methods, each necessary substance can be added to the photosensitive layer. The present invention can be used in various applications. Examples include printing plates, proofs, photographic paper, photosensitive materials for photography, hard copies of video signals, facsimile recording materials, CRT recording materials, copying materials, OHP films, etc. In either application, images can be recorded using only dry processing with significantly higher sensitivity than conventional non-silver salt recording materials (and if a dry processing method is used to visualize the polymer image), and Compared to the case of using a silver salt photographic material, when the material of the present invention is used, although the sensitivity is the same, the amount of silver used is greatly reduced and it is cheaper, and images can be obtained by dry processing. It has this great feature. Example 1 Pentaerythritol tetraac 2.3g Lylate phthalocyanine 0.1g Methylene chloride 3.0g 8% by weight aqueous solution of polyvinyl alcohol (average polymerization 18.0g degree approximately 500) p-dodecylbenzenesulfon 0.8g Consisting of 5% by weight aqueous solution of sodium chloride The mixed solution was emulsified for 1 hour using an ultrasonic emulsifier to prepare a monomer emulsion. 6.6g of benzotriazole and 14g of gelatin in water
Silver nitrate 8.5% dissolved in 1500ml and stirred at 40°C.
Add a solution of g dissolved in 50 ml of water over 2 minutes, then
Adjust the pH to precipitate benzotriazole silver,
Remove unnecessary salt and finally adjust the pH to 6.0 to reduce the yield.
200g of benzotriazole silver emulsion was prepared. The coating solution was prepared as follows.

[Table] This was coated on a polyethylene terephthalate film to a dry film thickness of approximately 5 μm and dried to produce a photosensitive material. The amount of coated silver was approximately 0.1 g/m ² in terms of silver. Step wedges (steps in optical density) in photosensitive materials
After image exposure for 5 seconds at an illuminance of 50 lux using a halogen lamp through a 0.3) filter, a polyethylene terephthalate film was placed on the photosensitive layer of the same material, and this was placed on a pot plate heated to 125°C. Heated for 7 seconds. Next, the film was peeled off from the photosensitive layer, and the photosensitive material was immersed in water at about 60°C and shaken for 30 seconds. A blue image was formed. Example 2 In Example 1, triethylenediamine 0.02
When the same procedure was carried out except that 0.03 g of triethanolamine was used instead of 0.0 g, almost the same image as in Example 1 was obtained. Example 3 The same procedure as in Example 1 was carried out except that 0.02 g of p-aminophenol was used instead of 0.03 g of 2,6-dichloro-p-aminophenol, and heating was performed at 110°C for 20 seconds. However, almost the same image as in Example 1 was obtained.

Claims (1)

[Scope of Claims] 1. A photosensitive material containing a photosensitive silver halide, a polymerizable vinyl monomer, a thermal polymerization initiator, and a reducing agent represented by the following general formula () is imagewise exposed and then uniformly heated. An image recording method characterized by forming a polymer image on unexposed areas. General formula () In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Represents a group selected from an alkyl group and a substituted alkyl group, and Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an aryl group, and a halogen atom. represents a group. The substitution position of the hydroxyl group on the benzene ring may be any of the ortho, meta and para positions.