JPH0683070A - Image forming method - Google Patents

Abstract

PURPOSE:To form a high contrast image excellent in transparency with a photosensitive material utilizing a color development reaction. CONSTITUTION:A photosensitive material having a photosensitive layer contg. at least silver halide, a reducing agent, a polymerizable compd. and one of two kinds of substances causing a color development reaction on the substrate is imagewise exposed, developed during or after the exposure and laminated on a sheet holding the other of the substances on the transparent substrate to form an image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a light-sensitive material capable of forming a color image on the light-sensitive material.

[0002]

2. Description of the Related Art A light-sensitive material having a light-sensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a support causes a latent image to be formed on the silver halide, and the polymerizable compound is polymerized correspondingly. The image forming method can be used. An example of this image forming method is Japanese Patent Publication No. 45-111149.
No. 47-20741, No. 49-10697, JP-A No. 57-138632, No. 57-142638,
57-176033, 57-21146, 58-107529, 58-121031, 5;
No. 8-169143. These methods form an image-like polymer compound by polymerizing a coexisting polymerizable compound (eg, vinyl compound) when developing exposed silver halide using a developing solution. . Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, Japanese Patent Laid-Open No. 61-69
062, 61-73145, 61-18364.
No. 0, No. 61-188535, No. 61-228441
Each of the publications describes a method capable of forming a polymer compound by a dry treatment. The above method uses a recording material (photosensitive material) in which a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder is carried on a support. is there.
The above-mentioned image forming method is a method of polymerizing the polymerizable compound in the part where the latent image of silver halide is formed.

Further, a method of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed is disclosed in JP-A-61 / 1986.
-183641, 61-260241, 62-
70836, 62-81635, JP-A 2-14
No. 1756, No. 2-141757, No. 2-20725
No. 4 and No. 2-262662.

As one embodiment of a light-sensitive material that can be used in the above-described image forming method, a light-sensitive material having a structure in which a silver halide and a polymerizable compound are contained in microcapsules is disclosed in JP-A-61-275742. Have been described. The light-sensitive material using the above-mentioned microcapsules (hereinafter, referred to as photosensitive microcapsules) has an advantage that a clear image, particularly excellent in sharpness can be obtained. On the other hand, the development and the polymerization reaction in the above image forming method proceed smoothly under alkaline conditions. Therefore, it is preferable to include a base or a base precursor as an image formation accelerator in the photosensitive layer of the photosensitive material. For a light-sensitive material characterized in that the light-sensitive layer contains a base or a base precursor, see JP-A-62-1640.
No. 41 specification.

When the base or the base precursor is added to the light-sensitive material using the above-mentioned photosensitive microcapsules, it is necessary to store the base or the base precursor in the photosensitive microcapsules because of the function of promoting the image formation of the base or the base precursor. It is preferable in terms. Japanese Unexamined Patent Publication No. 64-322
No. 51, Japanese Patent Application Laid-Open No. 1-263641, Japanese Patent Application No. 1-1
No. 82245, Japanese Patent Application No. 1-160148 and the specification describe a photosensitive material using a photosensitive microcapsule characterized by containing a base or a base precursor in its content.

As an image forming method using a photosensitive material using these photosensitive microcapsules, a method of transferring an image on the photosensitive material to an image receiving material is generally used. On the other hand, in the above-mentioned transfer type image forming method, there is a problem such as disposal of the photosensitive material after transfer, and therefore it has been desired to form a monosheet. Regarding the mono-sheet type light-sensitive material, JP-A-62-
No. 209444 and JP-A-63-2613483. In the light-sensitive materials described in these documents, one of the two component substances that cause a color-forming reaction in a contact state is contained in the microcapsules and is isolated from the other components, so that color formation is suppressed. At the time of image formation, the microcapsules are destroyed so that two-component contact can be realized and a color image can be obtained.

The problem with the above-mentioned light-sensitive material is that since two components that cause a color-developing reaction are present on the same light-sensitive material, for example, when the light-sensitive material is stored under high temperature and high humidity, color is gradually developed. There was a problem that it would end up. Further, if the microcapsules are destroyed during the processing or use of the light-sensitive material, there is a problem that color is developed and stains on a white background portion when an image is formed are conspicuous. In order to solve the above problems, the present inventors have studied to strengthen the wall of the microcapsule and to sufficiently isolate the two color-forming components, but the color density required for image formation cannot be obtained. There was a problem such as. Further, when a transmission image is obtained using the above-mentioned light-sensitive material, it lacks transparency, and thus it is unsuitable as a light-sensitive material for OHP or medical (for X-ray, ultrasonic diagnosis, etc.).

[0009]

SUMMARY OF THE INVENTION Therefore, the problem to be solved by the present invention is to provide a transmission image which is superior to the conventionally known monosheet in terms of storability and transparency without waste of photosensitive material. Especially.

[0010]

[Means for Solving the Problems] The above-mentioned problems are as follows (1)
The image forming method shown in FIG. In addition, (2) to (4) are mentioned as preferred embodiments.

(1) At least silver halide on a support,
A reducing agent, a polymerizable compound and a photosensitive material having a photosensitive layer containing one of two types of substances that cause a color reaction, a development process is performed simultaneously with or after imagewise exposure,
Next, an image forming method characterized in that another sheet having the other substance which causes the above-mentioned color forming reaction on a transparent support is laminated on the above-mentioned photosensitive material for developing agent.

(2) The above-mentioned polymerizable compound and one of the two kinds of substances that cause a color reaction are in the form of oil droplets, or
The image forming method according to (1) above, which is contained in the photosensitive layer in a state of being contained in microcapsules.

(3) The silver halide, the reducing agent, the polymerizable compound, and one of the two kinds of substances that cause a color forming reaction are applied to the photosensitive layer in the form of oil droplets or in a state of being contained in microcapsules. The image forming method according to claim 1, wherein the image forming method is included.

(4) Among the two kinds of substances that cause a color forming reaction, the substance contained in the photosensitive layer is a colorless color developing agent, and the other substance contained in another sheet is a color developing agent. The image forming method according to claim 1.

As is apparent from the above description, the feature of the present invention is that two kinds of substances that cause a color reaction upon contact are divided into a light-sensitive material and a separate sheet, respectively, and both are laminated at the time of image formation. Is to accelerate the color reaction in the uncured portion of the polymerizable compound to obtain a color image. As a result, it is possible to completely eliminate the undesired color development before image formation, which is a drawback of the conventional monosheet type photosensitive material. Further, since the image is sandwiched by the support even after the image formation, the environmental dependence and the influence of scratches are smaller than those of the conventional type.

The two types of substances (called color image forming substances) which cause a color reaction in the contact state used in the present invention will be described below. As the color image-forming substance, there is used a substance which is colorless or light in itself, but develops color by contact with another component.

Examples include various systems that develop color by an acid-base reaction between two or more components, a redox reaction, a coupling reaction, a chelate-forming reaction and the like. For example, a color-developing system comprising a color-forming agent having a partial structure such as lactone, lactam, and spiropyran used in pressure-sensitive paper and an acidic substance (developing agent) such as acid clay and phenols; aromatic diazonium salt or diazotate, System utilizing azo coupling reaction of diazo sulfonates with naphthols, anilines, active methylenes; reaction of hexamethylenetetramine with ferric ion and gallic acid, phenolphthalein-complexons and alkaline earth A chelate forming reaction such as a reaction with a metal ion; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

Also, as another example of a system which develops a color by a reaction between two components, a case where this reaction proceeds by heating is known. In this case, it is necessary to heat the two components at the same time when the two components are mixed by breaking the microcapsules during pressurization or immediately after pressurization.

Examples of the color-developing agent in the color-developing agent / developing agent system include (1) triarylmethane-based compounds, (2) diphenylmethane-based compounds, (3) xanthene-based compounds, (4) thiazine-based compounds, and (5) spiropyran-based compounds. There are, for example, those described in JP-A-55-27253 and the like. Among them, (1) triarylmethane-based and (3) xanthene-based color formers are preferable because many of them have less fog and give high color density. Specific examples include crystal violet lactone, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane, 3
-Diethylamino-6-methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino −
7-o-chloroanilinofluorane and the like, which are used alone or in combination.

As the color developer, a phenolic compound, an organic acid or a metal salt thereof, an oxybenzoic acid ester, acid clay, etc. are used.

An example of a phenol compound is 4,4 '.
-Isopropylidene-diphenol (bisphenol A), p-tert-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-
Methylene-bis (2,6-di-tert-butylphenol), p-phenylphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4
-Hydroxyphenyl) -2-ethylhexane, 2,2
-Bis (4-hydroxyphenyl) butane, 2,2'-
Methylenebis (4-tert-butylphenol), 2,
2'-methylenebis (α-phenyl-p-cresol)
Thiodiphenol, 4,4′-thiobis (6-tert-butyl-m-cresol) sulfonyldiphenol, p-tert-butylphenol-formalin condensate,
Examples include p-phenylphenol formalin condensate.

Examples of the organic acid or its metal salt include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, o-toluic acid, p-toluic acid, salicylic acid and 3
-Tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3,
5- (α-methylbenzyl) salicylic acid, 3-tert-octylsalicylic acid and their zinc, lead, aluminum salt, magnesium salt, nickel salt and the like are useful. In particular, the salicylic acid derivative and its zinc salt or aluminum salt are excellent in terms of color developing ability, fastness of a color image, storability of a recording sheet, and the like.

Examples of the oxybenzoic acid ester include ethyl p-oxybenzoate, butyl p-oxybenzoate and p-
Examples include heptyl oxybenzoate and benzyl p-oxybenzoate.

The present invention particularly preferably utilizes the color former / developer system described above. Other color formers / color formers include, for example, phenolphthalein, fluorescein, 2 ', 4', 5 ', 7'-tetrabromo-3,4,5,6-tetrachlorofluorescein. In, tetrabromophenol blue, 4, 5, 6, 7
-Tetrabrophenolphthalein, eosin, aurincresol red, 2-naphtholphenolphthalein and the like.

As the color developer, inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines,
Examples thereof include nitrogen-containing compounds such as piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea,
Methylthiourea, allylthiourea, ethylenethiourea,
2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2
-Imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-ditolylguanidine, 1,2-dicyclohexyl Guanidine, 1,2-dicyclohexyl-3-phenylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetic acid Salt, 2-amino-benzothiazole, 2-
There is benzoylhydrazino-benzothiazole.

The color image-forming substance of the present invention is used in an amount of 0.5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the polymerizable compound. The color developer is used in a proportion of about 0.3 to 50 parts by weight with respect to 1 part by weight of the color developing agent.

When forming a full-color image,
A plurality of color development systems as described above may be used. In this case, a full-color image can be formed by combining at least three kinds of silver halide emulsions having photosensitivity in different spectral regions and encapsulating a coloring agent in each microcapsule so as to correspond to each emulsion. .

In the present invention, one of the above-mentioned color image forming substances is provided in the photosensitive layer of the photosensitive material and the other is provided on another sheet. When the color image-forming substance is a combination of a color-developing agent / developing agent (the most desirable system in the present invention), it is desirable to provide the color-developing component on the photosensitive layer and the developer component on a separate sheet.

The constituent components of another sheet will be described below. The separate sheet is prepared by coating the above-mentioned color image forming substance in the form of a particle dispersion layer or a molecular dispersion layer on one surface of a transparent support. When the color image-forming substance is a developer, it is preferable that the softening point is in the range of 80 ° C to 160 ° C in order to improve the transparency of the image. On a separate sheet, in addition to the color image forming substance, a thermoplastic substance in a particle dispersed state, or
It may be used in a molecularly dispersed state, and the transparency of the image is further improved.

Typical examples of the thermoplastic material used in the present invention are shown below, but their softening points are from 10 ° C to 200 ° C.
Is preferable, and 60 ° C. to 160 ° C. is more preferable. Typical specific examples include general thermoplastic polymers, polyethylene (preferably amorphous), ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, ethylene-acrylic ester copolymer, Ethylene-methacrylic ester copolymer, polypropylene (preferably amorphous), polystyrene, poly α-methylstyrene, α-methylstyrene-
Vinyltoluene copolymer, styrene-butadiene copolymer, styrene-methylmethacrylate copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile copolymer, styrene-acrylate copolymer, polymethylacrylate, polymethylmethacrylate , Polyethyl acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, methyl methacrylate-methacrylate copolymer, 2-ethylhexyl acrylate-methacrylate copolymer, ethyl acrylate-acrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer Combined, polyvinyl acetate, vinyl acetate-vinyl chloride copolymer, polyvinyl chloride, polyvinylidene chloride, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-a Rironitoriru copolymers, polyacrylonitrile, polyamides, polyesters, polyvinyl butyral, polyvinyl formal, polyurethane, ethyl cellulose, a cellulose acetate or the like.

As the low molecular weight thermoplastic resin, those used in hot melt type adhesives and the like can be used. Rosin and rosin modified resin, hydrogenated rosin, styrene modified polyterpene resin, styrene modified petroleum resin, petroleum-based Unsaturated hydrocarbon, styrene resin, terpene-phenol,
Examples thereof include aliphatic hydrocarbon resins, cyclopentadiene resins, modified phenol resins, alkylphenol resins and alkylphenol-acetylene resins.

Each of the above-mentioned thermoplastic substances is used alone or
You may use it in combination of 2 or more types. The present invention is not limited to the above as long as it has thermoplasticity. In addition, a binder for fixing the above-mentioned color image-forming substance to the support and a surfactant for coating may be used on the separate sheet. With respect to these, the same materials as those used for the light-sensitive material described later can be used.

Next, as a transparent support used for another sheet, a plastic base such as polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, polyimide or a glass sheet is used. However, the present invention is not limited to these.

Next, the light-sensitive material relating to the present invention will be described. The light-sensitive material has a light-sensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound and the above-mentioned color image-forming substance on a support. The substance is generally contained in the photosensitive layer in a state of being encapsulated in oil droplet particles or microcapsules. At this time, the silver halide as a photosensitive component is appropriately
It is placed inside / outside or at the interface of oil droplet particles or microcapsule particles. When a full-color image is obtained, photosensitive microcapsules containing a polymerizable compound, a color image-forming substance and silver halide and having different photosensitive wavelengths are used in the photosensitive layer.

The silver halide, reducing agent, polymerizable compound, image forming accelerator, microcapsule, support and other components used in the light-sensitive material for image formation of the present invention will be described below. In the light-sensitive material of the present invention, as silver halide, any grains of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide are used. be able to. The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra, dodecahedrons and tetradecahedrons, grains having an irregular crystal system such as spheres and plates. It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.01 micron or less, but the projected area diameter is about 1
Large grains up to 0 micron may be used, and polydisperse emulsions may also be used in US Pat. Nos. 3,574,628 and 3,574.
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in the publications may be used.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Engineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157. 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 a compound other than silver halide such as silver rhodanide and lead oxide. Further, two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types"
, And ibid. 18716 (November 1979), 6
It can be prepared using the method described on page 48 and the like. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below. Known photographic additives that can be used in the present invention are also the above-mentioned two research products.
It is described in the disclosure, and the relevant parts are shown in the table below.

Additive type RD17643 RD18716 Chemical sensitizer, page 23, page 648, right column, sensitivity enhancer, same as above, spectral sensitizer, page 23-24, page 648, right column-supersensitizer, page 649, right column, antifoggant 24- See page 25, page 649, right column and stabilizers. For details of the above silver halide emulsion and photographic additives, refer to "Public Technology No. 5" (Aztec Co., Ltd.,
(Published March 22, 1991) 2 to 17 pages. The amount of silver halide used is 0.001 to 10 g, preferably 0.05 to ² g, in terms of silver per 1 m ² of the light-sensitive material. Further, in the present invention, an organic silver salt can be used together with silver halide. The organic silver salt is described on pages 17 to 18 of "Public Technology No. 5" mentioned above.

The reducing agent which can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones and 5-amino. Uracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o-
Or p-sulfonamidophenols, o- or p
-Sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. The various reducing agents described above are described in detail on pages 18 to 35 of the above-mentioned "Known Technology No. 5". The addition amount of the reducing agent can be widely varied, but it is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. The compound having an ethylenically unsaturated group that can be used in the light-sensitive material, acrylic acid and its salts, acrylic acid esters,
Acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-
Examples include vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of preferable polymerizable compounds that can be used in the light-sensitive material include acrylic acid esters, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl. Acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate,
2- (2-hydroxy-1,1-dimethylethyl) -5
-Hydroxymethyl-5-ethyl-1,3-dioxane acrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-dioxane triacrylate, propylene of trimethylolpropane Examples thereof include triacrylate of an oxide adduct, hexaacrylate of a caprolactone adduct of dipentaerythritol, polyacrylate of hydroxypolyether, polyester acrylate and polyurethane acrylate.

As other specific examples, regarding methacrylic acid esters, methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples thereof include pentaerythritol tetramethacrylate and dioxymethacrylate of polyoxyalkylenated bisphenol A.

The above 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, see JP-A-62-210445.
It is described in the official gazette. 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 described above can also be used as the polymerizable compound.

Next, in the light-sensitive material of the present invention, a base precursor can be used as an image formation accelerator. The base precursor that can be used in the light-sensitive material of the present invention,
Base precursors of inorganic bases and organic bases (such as decarboxylation type, thermal decomposition type, reaction type and complex salt forming type) can be used. For details of these base precursors and techniques for using them, see "Public Technology No. 5", pp. 55-86.
Page.

Preferred base precursors are JP-A Nos. 59-180549, 59-180537, 59-195237, 61-32844 and 61.
-36743, 61-51140, 61-52.
No. 638, No. 61-52639, No. 61-53631.
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
53638, 61-53639, 61-536.
40, 61-55644, 61-55645.
No. 61, No. 61-55646, No. 61-84640, No. 61-107240, No. 61-2119950, No. 6
1-251840, 61-252544, 61
-313431, 63-316740, 64-
No. 68746 and Japanese Patent Application No. 1-54452, salts of organic acids and bases that are decarboxylated by heating.
Further, JP-A-59-157637 and JP-A-59-1669.
The compounds described in JP-A-43-63 and JP-A-63-96159, which eliminate a base by heating, can be mentioned.

The base precursor of the present invention is 50
It is preferable to release the base at ℃ to 200 ℃, 80
More preferably, the release is carried out at a temperature of 180 ° C to 180 ° C. The base precursor used in the light-sensitive material of the present invention is disclosed in Japanese Patent Application No.
A base precursor consisting of a salt of a carboxylic acid and an organic base having a solubility of 1% or less in water and a polymerizable compound at 25 ° C. as described in JP-A-270159 is particularly preferable.

In the present invention, when the base precursor is contained in the oil droplets of the polymerizable compound or contained in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in the polymerizable compound may be used. Kaisho 64-3
No. 2251, JP-A-1-263641).
It is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (JP-A-63-218964, Japanese Patent Application No. 1-18
No. 2245, Japanese Patent Application No. 1-160148 and each description) In the dispersion of the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Further, as the amphoteric water-soluble polymer,
Mention may be made of gelatin.

The above water-soluble polymer is preferably contained in the base precursor in a proportion of 0.1 to 100% by weight, more preferably 1 to 50% by weight. The base precursor is preferably contained in the dispersion in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight. Further, the base precursor is preferably contained in a proportion of 2 to 50% by weight with respect to the polymerizable compound,
It is more preferable that the content is 5 to 30% by weight.

No particular limitation is imposed on the encapsulation method that can be used for the photosensitive microcapsules of the present invention, and various known techniques can be applied.
It is described in detail on pages 88 to 98. In the present invention, it is particularly preferable to use a melamine-formaldehyde resin, since a highly dense capsule can be obtained. Further, JP-A-2-216151 discloses a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group in order to obtain a capsule having particularly excellent wall compactness. A microcapsule in which a polymer wall of a high molecular compound such as melamine / formaldehyde resin is provided around the membrane is disclosed, which is preferable for the present invention.

When aminoaldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in JP-A-63-32535. The method is disclosed in JP-A-63-14.
No. 2343, etc.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably not more than one fifth of the average size of the microcapsules, and preferably not more than one tenth. More preferably, By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.
When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding a light-sensitive material containing silver halide in the wall material of microcapsules, JP-A-62-62
No. 169147.

In the production of the photosensitive microcapsules of the present invention, an oily liquid composed of a silver halide, a reducing agent, a color image-forming substance, and a polymerizable compound containing a base precursor is dispersed in an aqueous medium to form a capsule shell. When forming a, it is preferable that the aqueous medium contains a nonionic water-soluble polymer and an anionic water-soluble polymer. In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight with respect to the aqueous medium,
˜90% by weight is more preferred.

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Examples of the anionic water-soluble polymer include polystyrene sulfinic acid, copolymer of styrene sulfinate, polystyrene sulfonate, copolymer of styrene sulfonate, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride. -Styrene copolymers, maleic anhydride / inbutylene copolymers and the like can be mentioned. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. In the above case, it is particularly preferable to use the nonionic water-soluble polymer in combination with the water-soluble polymer having a small amount of sulfinic acid groups.

Further, in order to reduce the solubility of the base precursor in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearamide, etc. are added to the polymerizable compound. OH, -SO ₂ NH _2, -CONH
_{It is} also possible to add a compound having a hydrophilic group such as ₂ , ₂ , -NHCONH ₂ .

In the present invention, in addition to the reducing agent, known antioxidants can be used together with the polymerizable compound for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during thermal development. As such an antioxidant, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, 2,
2'-butylidene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methylphenyl acrylate, 4,4'-thio-bis- (3-methyl-6-t-butylphenol) and other phenolic antioxidants; diphenyldecyl phosphite,
Triphenyl phosphite, tris- (2,4-di-t
-Butylphenyl) phosphite, tris- (2-ethylhexyl) phosphite and other phosphite antioxidants; dilauryl-3,3'-thio-dipropionic acid ester, pentaerythritol-tetrakis- (β-lauryl-thio -Psupionate ester), thio-dipropionic acid and other sulfur-based antioxidants; phenyl-1-naphthylamine, 6-ethoxy-2,2,4-trimethyl-
Examples include amine antioxidants such as 1,2-dihydroquinoline and dioctyliminodibenzyl.

Materials usable for the support include glass, paper, woodfree paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose. Ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, and paper laminated with a resin material or a polymer such as polyethylene. For details, refer to “Public Technology No. 5” above.
No. "pp. 144-149. When it is desired to obtain a transmission image using the present invention, for example, when it is used as a light-sensitive material for OHP or medical (for X-ray, ultrasonic diagnosis, etc.), it is necessary to select a transparent support.

Other components that can be used in the light-sensitive material of the present invention will be described below. Details of these components are described in the above-mentioned "Known Technology No. 5", pp. 98-144 and 86-.
It is described on page 88. The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical. For example, natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Synthetic polymers such as water-soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed polyvinyl compounds in the form of latices, which in particular increase the dimensional stability of photographic materials. The light-sensitive material using a binder is described in JP-A-61-69062. Further, regarding a light-sensitive material using a binder together with microcapsules, see JP-A-62-209525.
It is described in the official gazette.

Other image forming accelerators can be used in the light-sensitive material.

The image forming accelerator has a function of promoting transfer of a base or a base precursor, promoting reaction of a reducing agent with a silver salt, and promoting immobilization of a dye-donor substance by polymerization. Are classified into the above-mentioned bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, compounds that interact with silver or silver salts, compounds having an oxygen scavenging function, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned accelerating effects together. Details thereof are described in the specifications and publications of U.S. Pat. No. 4,678,739, columns 38 to 40, JP-A-62-209443 and the like. The hexavalent metal compound described in Japanese Patent Application No. 2-272878 is also effective.

In the system for polymerizing the polymerizable compound in the portion where the latent image of silver halide is not formed,
A heat or photopolymerization initiator can be used for the purpose of initiating polymerization or for polymerizing an unpolymerized polymerizable compound after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids and the like. Details thereof are described in pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science, Editorial Committee for Polymer Experiments.

Examples of the photopolymerization initiator include benzophenones, acetophenones, benzoins, thioxanthones and the like. Details thereof are described in "UV Curing System" (1989, Comprehensive Technical Center), pages 63 to 147, and the like. Various surfactants may be used in the light-sensitive material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-17.
No. 3463, No. 62-183457 and the like. An antistatic agent can be used in the light-sensitive material for the purpose of antistatic. As an antistatic agent, Research Disclosure, November 1978, No. 17643 (27
Page) etc.

A dye having a property of being decolorized by heating or light irradiation may be contained in the photosensitive microcapsule. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. Regarding a light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above, Japanese Patent Laid-Open No.
It is described in JP-A-3-974940.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-168442.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used. .

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. 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. More specifically, JP-A-62-253159, pages (31) to (32), JP-A-1-724
No. 79, No. 1-3471, etc. are described.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the specification of the above-mentioned series of photosensitive materials, and Research Disclosure Vol.
No. 17029, June 1978 (pages 9 to 15). As the layer that can be optionally provided in the photosensitive material,
Examples thereof include a heating element layer, an antistatic layer, an anti-curl layer, and a peeling layer.

A light-sensitive material using a heating element layer is described in JP-A-61-294434.
Furthermore, regarding other examples of auxiliary layers and their usage modes,
It is described in the specification of the application relating to the series of photosensitive materials described above.

Next, in the image-forming method of the present invention, an imagewise exposure step, simultaneously with the imagewise exposure, or after the imagewise exposure,
The step of heating the photosensitive material from the surface of the support not coated with the photosensitive layer and the step of laminating the photosensitive material on another sheet will be described. As the exposure method in the imagewise exposure step, various exposure means can be used, but in general, a latent image of silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure can be selected according to the photosensitive wavelength of silver halide (wavelength sensitized when dye sensitization is performed) and sensitivity.

Typical light sources include low-energy radiation sources such as natural light, ultraviolet light, visible light, infrared light, fluorescent lamps, tungsten lamps, mercury lamps, halogen lamps, xenon flash lamps, laser light sources (gas laser, solid laser, Chemical lasers, semiconductor lasers, etc.), light emitting diodes, plasma arc tubes, FOTs and the like. In special cases, it is possible to use X-rays, γ-rays, electron beams, etc., which are high energy ray sources.

The light-sensitive material of the present invention, particularly in the case of a full-color light-sensitive material, is composed of microcapsules having photosensitivity in a plurality of spectral regions, and therefore it is necessary to perform image exposure with a plurality of corresponding spectral lines. Is. Therefore, the above light sources may be used alone or in combination of two or more. When selecting the light source,
It goes without saying that a light source suitable for the photosensitive wavelength of the photosensitive material is selected, but it can be selected in consideration of whether image information passes through an electric signal, the processing speed of the entire system, compactness, power consumption, and the like.

When the image information does not pass through an electric signal, for example, direct photographing of landscapes and people, direct copying of original images,
In the case of exposing through a positive such as a reversal film, an exposure device for printing such as a camera, a printer or an enlarger, an exposure device for a copying machine or the like can be used. In this case, a two-dimensional image can be simultaneously exposed by so-called one shot, or scanning exposure can be performed through a slit or the like. You can also stretch or reduce the original image. In this case, the light source is not a monochromatic light source such as a laser but a light source such as a tungsten lamp or a fluorescent lamp, or a combination of a plurality of monochromatic light sources.

When image information is recorded via electric signals, a light emitting diode and various lasers may be used in combination as the image exposure device in accordance with the color sensitivity of the heat-developable color photosensitive material. Various devices known as image display devices (CRT, liquid crystal display, electroluminescent display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information is an image signal obtained from a video camera or an electronic still camera, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels with a scanner or the like, or an image signal stored in a recording material such as a magnetic tape or a disk can be used.

When exposing a color image, LEDs, lasers, fluorescent tubes and the like are used in combination according to the color sensitivity of the light-sensitive material. However, the same materials may be used in combination, or different materials may be used in combination. May be. The color sensitivity of the light-sensitive material is R (red), G (green), B (blue) in the photographic field.
Photosensitivity is normal, but in recent years, it is often used in combination with UV, IR, etc., and the range of use of the light source is expanding. For example, the color sensitivity of the photosensitive material is (G, R, IR)
Or (R, IR (short wave), IR (long wave)),
(UV (short wave), UV (medium wave), UV (long wave)), (U
Spectral regions such as V, B, G) are utilized. The light source may also be a combination of different types such as a combination of two LED colors and a laser. The light emitting tube or element may be scanned and exposed by using a single tube or element for each color, or an array tube may be used to increase the exposure speed. Examples of usable arrays include an LED array, a liquid crystal shutter array, and a magneto-optical element shutter array.

The image display device described above is a CRT.
As described above, there is a color display and a monochrome display, but a method of performing exposure several times by combining a color display with a color filter may be adopted. Existing 2
The three-dimensional image display device may be used by making it one-dimensional like FOT, or by dividing one screen into several pieces and using them in combination with scanning. By the above imagewise exposure, a latent image is obtained on the silver halide contained in the microcapsules. The image forming method of the present invention includes a step of heating the photosensitive material at the same time as the imagewise exposure or after the imagewise exposure to thermally develop the photosensitive material. Thermal development is preferably performed by heating from the surface of the support on which the photosensitive layer of the photosensitive material is not coated.

As this heating means, there is disclosed in JP-A-61-29.
As in the light-sensitive material described in Japanese Patent No. 4434, a heating element layer may be provided on the surface of the support on which the light-sensitive layer of the light-sensitive material is not coated to heat it. Further, as described in JP-A-61-147244, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heat roller and a belt. You may use the method of heating.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than the area of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (heating plate,
The entire surface may be heated over time by bringing it into contact with a heat roller, a heat drum, etc. and scanning it.
In addition to the heating method in which the heating element and the photosensitive material are brought into direct contact with each other as described above, electromagnetic waves, infrared rays, hot air or the like can be applied to the photosensitive material to heat it in a non-contact state.

In the image forming method of the present invention, thermal development is carried out by heating the surface of the photosensitive material on the support on which the photosensitive layer is not coated. At this time, the photosensitive layer is coated. The surface that is marked may be in direct contact with the air,
It may be covered with a heat insulating material or the like in order to keep it warm so as not to release heat. In this case, it is preferable not to apply a strong pressure (10 kg / cm ² or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer. Further, the heat development by heating is carried out simultaneously with or after the imagewise exposure, but it is preferable to perform the heating after 0.1 seconds or more has passed after the imagewise exposure. Heating temperature is generally 60 ℃
To 250 ° C, preferably 80 ° C to 180 ° C,
The heating time is between 0.1 and 20 seconds, preferably between 0.5 and 5 seconds.

The photosensitive material can be subjected to heat development as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. When a polymerization inhibitor is formed in the latent image-formed portion of silver halide by the reaction with a reducing agent, heat or photopolymerization initiation which has been added in advance in the photosensitive layer, preferably in the microcapsules. It is also possible to decompose the agent by heating or irradiating it with light to uniformly generate radicals and polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed. In this case, in addition to the above-mentioned imagewise exposure step and heat development step, if necessary, a whole surface heating or whole surface exposure step is required, and the method is the same as the imagewise exposure step or the heat development step.

In the image forming method of the present invention, the above-mentioned light-sensitive material having a polymer image formed on the light-sensitive layer is laminated on another sheet and laminated to form a color image-forming substance (for example, a color former) in the uncured portion. A color image forming substance (for example, a color developer) on another sheet is brought into contact with and reacted with. As a result, a transparent color image can be obtained on the photosensitive material. For the above-mentioned laminate, a method of stacking both sheets and applying pressure or applying pressure while heating is used.

For example, the photosensitive material and another sheet may be stacked and sandwiched between press plates such as a presser, or pressure may be applied while being conveyed using a pressure roller such as a nip roll. In the above case, the pressure required for pressurization is 300 kg / cm ² or more, preferably 600 kg / cm ² or more. In the case of the image forming method of the present invention, heating (40 ° C. to 18 ° C.) is applied by the above pressure method.
0 ° C.) is more preferable, and in this case, it is 30
Sufficient transparency can be obtained at a pressure of 0 kg / cm ² or less. or,
There is also an advantage that color development becomes faster. Further, the heating temperature may be changed to pressurize and heat twice or more.

The light-sensitive material of the present invention is a black-and-white or color light-sensitive material for photography and printing, a light-sensitive material for printing, a plate, a computer graphic hard-copy light-sensitive material, a light-sensitive material for copying machines, a medical light-sensitive material (for roentgen, For ultrasonic diagnostic CRT)
In addition, the image forming method of the present invention is suitable for forming an image forming system such as a compact and inexpensive copying machine, printer, and simple printing machine.

[0082]

【Example】

Example 1 Preparation of Photosensitive Material (A) Preparation of Silver Halide Emulsion (EG-1) 24 g of lime-processed inert gelatin was added to 900 cc of distilled water, dissolved at 40 ° C. for 1 hour, and 3 g of NaCl was added thereto, and 1N was added thereto. The pH was adjusted to 3.2 by adding sulfuric acid.

After 10 mg of (AGS-1) was added to this solution, the solution I and the solution II were kept at 60 ° C. by the control double jet method while keeping pAg = 8.5, and at the same time, it took 15 minutes until the solution I disappeared. Added. After the addition is complete, p
H was adjusted to 6.0 with 1N NaOH and (AZ-1) 6.
4 mg and (AZ-2) 4.8 mg were added to 60 at 60 ° C.
Aged. After the aging, 450 mg of (SG-1) was added, and 100 g of an aqueous solution containing 4.1 g of KI was added at an equal flow rate over 20 to 30 minutes after the addition.

To this emulsion, 1.1 g of poly (isobutylene-monosodium coumarate) was added, precipitated, washed with water, desalted, and then added with 6 g of lime-processed gelatin to dissolve, and further 3.5 of (ATR-3). % Aqueous solution (1.5 cc) was added to adjust the pH to 6.2. Average particle size 0.18
Monodispersed silver iodobromide emulsion (EG-
1) 550 g was prepared.

Liquid I AgNO ₃ 120 g Distilled water 550 cc Liquid II KBr 85 g Distilled water 550 cc

[0086]

[Chemical 1]

Preparation of solid dispersion (KB-1) 5.4 of lime-processed gelatin in a 300 ml dispersion container.
% Aqueous solution 110 g, polyethylene glycol (average molecular weight 2000) 5% aqueous solution 20 g, base precursor (BG-1) 70 g, and glass beads 200 ml having a diameter of 0.5 to 0.75 mm are added, and 300 using a Dynomill.
Disperse at 0 rpm for 30 minutes, adjust to pH 6.5 with 2N sulfuric acid.
Adjusted to 1.0 μm or less and a base precursor (B
A solid dispersion (KB-1) of G-1) was obtained.

[0088]

[Chemical 2]

Preparation of Coloring Agent Solution (DS) To 255 g of the following polymerizable compound (MN-1), 38 g of the following black type coloring agent (D-1) was mixed and stirred at 80 ° C. for 1 hour,
A color former solution (DS) was prepared. Polymerizable compound (MN-1) Compound described in Synthesis Example 1 of JP-A-64-68339 (manufactured by Nippon Kayaku Co., Ltd.)

[0090]

[Chemical 3]

Preparation of Photosensitive Composition (DG-1) 194 g of color developer solution (DS) was added with (SV- of 1P-4).
1) 36 g of 10% (wt%) solution, (RD-1) 4.
6 g, (RD-3) 12.4 g, (FF-3) (SV
-1) 8 cc of 0.5% (wt%) solution and 2 g of polyethylene glycol 2000 were added and dissolved to prepare an oily solution. A silver halide emulsion (EG-
1) 50 g and 96 g of solid dispersion (KB-1) were added,
While maintaining the temperature at 60 ° C., a 50φ dissolver was used to stir at 7,000 rpm for 5 minutes to obtain a photosensitive composition (DG-1) as a W / O emulsion.

[0092]

[Chemical 4]

Preparation of Photosensitive Microcapsule Dispersion Liquid (A) 18 g of a 12% aqueous solution of polymer (2P-4) was added to 20 g of water.
2 g was added and the mixed solution was adjusted to pH 5.0 with 1N sulfuric acid. A 10% aqueous solution of polymer (2P-2) 18
0 g was added and mixed at 60 ° C. for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (DG-1) and stirred at 60 ° C. at 8000 rpm for 10 minutes using a 50φ dissolver to obtain an emulsion in the state of W / O / W emulsion. Separately, 52.2 g of a 37% aqueous solution of formaldehyde and 170.3 g of water were added to 31.5 g of melamine, heated to 60 ° C., and stirred for 30 minutes to obtain a transparent aqueous solution of a melamine-formaldehyde initial condensation product.

132 g of this initial condensate was added to the emulsified product in the state of W / O / W emulsion cooled to 40 ° C., and it was stirred with a propeller blade at 1200 rpm for 1N.
32 cc of sulfuric acid was added. This solution is then 70 minutes for 30 minutes.
The temperature was raised to 0 ° C., and the mixture was further stirred for 30 minutes. To this was added 54 g of a 40% aqueous solution of urea, 24 cc of 1N sulfuric acid was added, and stirring was continued at 70 ° C. for another 40 minutes. After this solution was cooled to 50 ° C., a 1N aqueous sodium hydroxide solution was added to adjust the pH to 6.5 to prepare a photosensitive microcapsule dispersion (A). The volume average particle size of the microcapsules measured by Coulter Multisizer II (Coulter) was 14.5 μm. Polymer (2P-2) Polyvinylpyrrolidone K-90 Polymer (2P-4) Potassium polyvinylbenzenesulfinate-co-acrylamide

Preparation of Photosensitive Material (A) 10 g of the above-mentioned photosensitive microcapsule dispersion liquid (A),
A coating solution was prepared by mixing 10 g of a 5% aqueous solution of sodium sulfosuccinate ester. The amount of liquid applied is 105cc /
Use a rod to make m ² and coat it on a polyester transparent base with a thickness of 100 μm and a gelatin undercoat.
The photosensitive material (A) was prepared by drying at 0 ° C.

Preparation of Separate Sheet (A) Preparation of Solid Developer Dispersion Liquid 30 g of the powder of the developer (DP-1) was mixed with 120 g of a 3% aqueous solution of polyvinyl alcohol (trade name; PVA-205, manufactured by Kuraray). 300 minutes per minute using a Dynomill disperser
Crushed and dispersed for 20 minutes at 0 rpm. The obtained liquid is used as a solid developer dispersion (DP-1). On the other hand, the color developer (DP
A liquid obtained by pulverizing and dispersing 30 g of the powder of -2) in the same manner is used as a solid developer dispersion (DP-2).

[0097]

[Chemical 5]

Preparation of Thermoplastic Resin Dispersion Liquid (A) Poly α-methylstyrene (trade name; Crystalrex 1
120, softening point 120 ° C, manufactured by Rika Hercules Co., Ltd.
The powder of (1) was roughly pulverized in an automatic mortar, and 60 g of this was taken and roughly dispersed in a mixed liquid of 120 g of a 1% aqueous solution of sodium salt of sulfosuccinate and 120 g of water. This crude dispersion is applied to an Eiger motor mill, 2000 r.p.
It was pulverized at m. for about 25 minutes to prepare a thermoplastic resin dispersion liquid (A) having an average particle diameter of about 1 μm.

Preparation of Separate Sheet (A) 10 g of the solid developer dispersion (DP-1) obtained above, 10 g of the solid developer dispersion (DP-2) and 10 g of the thermoplastic resin dispersion (A) were prepared. The mixed solution was applied onto a transparent polyester base (thickness: 66 μm) with a gelatin undercoat so that the applied amount of the solution was 105 cc / m ² , and another sheet (A) was prepared. Evaluation of Photosensitive Material (A) The photosensitive material (A) was passed through a wedge whose density continuously changed from 0 to 3.0, and a tungsten light bulb was used to measure 20.
After imagewise exposure at 00 lux for 1 second, it was placed on a hot plate heated to 140 ° C. and heated for 10 seconds. Then, the coating layer of the above-mentioned separate sheet (A) was superposed on the photosensitive layer, passed through a heating roller at 50 ° C. under a pressure of 150 kg / cm ² , and then 1
It was passed between a pair of rollers heated to 50 ° C. As a result, a clear and clear image was obtained.

Example 2 Preparation and Evaluation of Photosensitive Material (B) Preparation of Silver Halide Emulsion (A-1) Gelatin aqueous solution (gelatin 1 in 1500 ml water was stirred).
6 g and 0.5 g of sodium chloride, which was adjusted to pH 3.8 with 1N sulfuric acid and further kept at 60 ° C.), and an aqueous solution 300 containing 71 g of potassium bromide.
ml and an aqueous solution of silver nitrate (0.59 mol of silver nitrate dissolved in 300 ml of water) were simultaneously added at an equal flow rate over 50 minutes. Ten minutes after this was completed, 100 ml of an aqueous solution containing 2.9 g of potassium iodide and an aqueous silver nitrate solution (0.018 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added over 5 minutes. Thus, a monodisperse tetradecahedral silver iodobromide emulsion having an average grain size of 0.22 μm was prepared. After washing the above emulsion with water and desalting,
0.5% of the following infrared sensitizing dye (IS-1) was added to this emulsion.
94 ml of a methanol solution and 2 of the compound (a) shown below
% Aqueous solution (75 ml) was added to obtain a silver halide emulsion (A-1) with a yield of 600 g.

[0101]

[Chemical 6]

Preparation of silver halide emulsions (A-2 to A-4) In the preparation of the above silver halide emulsion (A-1), instead of the infrared sensitizing dye (IS-1), the following red Same as the preparation of the silver halide emulsion (A-1), except that the external sensitizing dyes (IS-2), (IS-3) and (IS-4) are used in the respective addition amounts shown in Table 1. By performing various operations, the silver halide emulsion (A-
2), (A-3) and (A-4) were prepared.

[0103]

[Chemical 7]

The respective silver halide emulsions thus obtained are summarized in Table 1 below. Table 1 Silver halide emulsion Infrared sensitizing dye Addition amount (ml) (0.5% methanol solution) A-1 (IS-1) 94 A-2 (IS-2) 145 A-3 (IS-3) 67 A-4 (IS-4) 85

Preparation of Photosensitive Material (B) In the preparation of the photosensitive composition of Example-1, instead of 50 g of silver halide emulsion (EG-1), the silver halide emulsion (A- 1) 20 g, (A-2) 10 g,
A light-sensitive material (B) was produced in the same manner except that a mixture of 10 g of (A-3) and 10 g of (A-4) was used.

Evaluation of Photosensitive Material (B) The photosensitive material (B) obtained above was processed and evaluated in the same manner as in Example-1. As a result, a transparent and clear image was obtained. However, during the exposure, the amount of exposure was adjusted by changing the voltage or the exposure time. Also,
When exposed using a laser diode having a peak wavelength of 780 nm and processed in the same manner, a transparent and clear image was obtained.

Example 3 Preparation of Photosensitive Composition (DG-2) 194 g of color former solution (DS) was added with (SV- of 1P-4).
1) 36 g of 10% (wt%) solution, (RD-1) 4.
6 g, (RD-3) 12.4 g, (FF-3) (SV
-1) 8 cc of 0.5% (wt%) solution was added and dissolved to prepare an oily solution. Silver halide emulsion (E
G-1) Add 35 g, and while maintaining the temperature at 40 ° C, 50φ
The mixture was stirred at 10,000 rpm for 5 minutes using a dissolver to obtain a W / O emulsion photosensitive composition (DG-2).

Preparation of Photosensitive Microcapsule Dispersion Liquid (C) To 35 g of the above photosensitive composition (DG-2), 5 g of Takenate D110N (Takeda Chemical Co., Ltd., polyvalent isocyanate) was added and well stirred. Next, add polyvinyl alcohol (PVA-217, made by Kuraray) to a 100cc homogenizer container.
50 g of a 4% aqueous solution of the above was added, and the above mixture was added thereto, followed by stirring at 8000 rpm for 5 minutes to obtain an emulsion. This emulsion was stirred at 40 ° C. for about 3 hours to prepare a photosensitive microcapsule dispersion (C).

Preparation of Photosensitive Material (C) 10 g of the photosensitive microcapsule dispersion liquid (C) obtained above
The solid dispersion (KB-1) prepared in Example 1 was added to 0.8
and 0.05 g of a surfactant (trade name: Emamarex NP-8, manufactured by Nippon Emulsion Co., Ltd.) were mixed to prepare a coating liquid. This was applied onto a polyester transparent base having a thickness of 100 μm and having an undercoat of gelatin and having a thickness of 52 cc / m ² so as to have a liquid coating amount of 52 cc / m ² , and dried at 50 ° C. to prepare a light-sensitive material (C).

Preparation of Separate Sheet (B) Separate sheet (B) was prepared in the same manner as in Preparation of separate sheet (A) of Example 1 except that 10 g of water was used instead of 10 g of the thermoplastic resin dispersion liquid (A). )made.

Evaluation of Photosensitive Material (C) Using the above-mentioned photosensitive material (C) and another sheet (B), the same evaluation as the photosensitive material (A) of Example 1 was carried out, and a clear image having good transparency was obtained. was gotten.

Example 4 Preparation of Coloring Agent Emulsion (EM) 51 g of the coloring agent solution (DS) prepared in Example 1 was mixed with 10 g of ethyl acetate. On the other hand, in a 200 ml homogenizer container, a mixed solution of 119 g of a 3% aqueous solution of PVA-217 and 6 g of a 5% aqueous solution of sodium dodecylbenzenesulfonate was added, and the color former solution was added thereto, and 8000 r.p.
Emulsified and dispersed at m. for 10 minutes to obtain a color developer emulsion (EM).

Preparation of solid dispersion (KB-2) 3% of PVA-205 in a Dynomill dispersion container.
Aqueous solution 180 g, reducing agent (RD-1) 20 g and glass beads 200 ml were added and dispersed at 3000 rpm for 30 minutes to obtain a reducing agent solid dispersion (KB-2).

Preparation of Photosensitive Material (D) The silver halide emulsion (EG-1) 0.
To 5 g, 0.05 g of a 0.5% (% by weight) solution of (SV-1) (FF-3) and a solid dispersion (KB-2) of 1.
6 g, 3 g of the solid dispersion (KB-1) and 12 g of the color developer emulsion (EM) were added, and the mixture was stirred at 40 ° C. for 15 minutes. This mixed solution was coated on a transparent polyethylene terephthalate film (thickness: 100 μm) with an undercoat so as to have a coating solution of 52 cc / m ² and dried to prepare a light-sensitive material (D).

Evaluation of Photosensitive Material (D) Using the above-mentioned photosensitive material (D) and the separate sheet (B) prepared in Example 3, the same evaluation as in the photosensitive material (A) of Example 1 was carried out. A clear image with good properties was obtained.

Comparative Example 1 Preparation of Photosensitive Material (E) The photosensitive microcapsule dispersion liquid (A) used in Example 1
Fluorosurfactant (trade name; Surflon S to 10 g)
-111, 2 g of a 30% aqueous solution of Asahi Glass Co., Ltd., and 3 g of a 3% aqueous solution of sodium polystyrene sulfonate were added, the mixture was stirred with a stirrer for 5 minutes, and then the solid developer dispersion liquid (DP) prepared in Example 1 was used. -1) and 10 g of the solid developer dispersion (DP-2) were added and well stirred. The coating solution thus obtained was coated in the same manner as in Example 1 so that the coating amount of the solution was 105 cc / m ² , to prepare a photosensitive material (E).

Evaluation of Light-Sensitive Material (E) The light-sensitive material (E) was passed through a wedge whose density continuously changes from 0 to 3.0, and a tungsten light bulb was used to measure 20.
After imagewise exposure at 00 lux for 1 second, it was placed on a hot plate heated to 140 ° C. and heated for 10 seconds. Then, after passing through a heating roller at a pressure of 150 kg / cm ² at 50 ° C., it was passed between a pair of rollers heated at 150 ° C. in a state of being overlapped with a silicone resin-coated release paper. Then, when the release paper was peeled off, an unclear image lacking transparency was obtained. In particular, stains on the white background corresponding to the exposed areas were noticeable.

As is apparent from Examples 1 to 4 and Comparative Example 1, when the two components that cause a color-developing reaction are separately used on the light-sensitive material and on a separate sheet, the white background portion due to breakage of the microcapsules is used. It was found that the stains on the sample were significantly reduced and the color image became clearer. Also, the transparency of the transmitted image was improved by laminating another sheet. In addition, several image sheets obtained in Examples 1 to 4 and Comparative Example 1 were stacked and pressed, and stored under high temperature and high humidity of 40 ° C. and 80% RH. However, in all the examples, no adhesion was caused.

Claims (4)

[Claims] 1. A photosensitive material having, on a support, a photosensitive layer containing at least a silver halide, a reducing agent, a polymerizable compound and one of two kinds of substances that cause a color reaction,
Development is carried out simultaneously with or after imagewise exposure, and then another sheet having the other substance causing the above-mentioned color reaction on the transparent support is laminated on the above-mentioned developing agent photosensitive material. Image forming method. 2. The polymerizable layer and one of the two kinds of substances that cause a color-forming reaction are contained in the photosensitive layer in an oil droplet state or in a state of being contained in microcapsules. The image forming method described. 3. A photosensitive layer containing silver halide, a reducing agent, a polymerizable compound, and one of two kinds of substances that cause a color reaction, in the form of oil droplets or contained in microcapsules. The image forming method according to claim 1, wherein: 4. Of the two types of substances that cause a color reaction,
The image forming method according to claim 1, wherein the substance contained in the photosensitive layer is a colorless color developing agent, and the other substance contained in another sheet is a color developing agent.