JPH0422509B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to an image recording method. More specifically, a photosensitive silver halide is used as a photosensor, microcapsules containing a polymerizable compound and a color image-forming substance are imagewise cured by heating, and at least a portion of the uncured microcapsules is then pressurized. The present invention relates to a recording method in which a polymerizable compound and a color image-forming substance are transferred to an image-receiving material. "Prior art" As an example of an image recording material using microcapsules containing a photosensitive composition,
A system is known in which a synthetic polymer resin wall capsule containing a vinyl compound, a photopolymerization initiator, and a colorant precursor is supported on a support, as disclosed in Japanese Patent No. 179836. The image recording method using this system is to imagewise harden the microcapsules by exposure to light, rupture the unhardened microcapsules by applying pressure, and obtain a color image from the released colorant precursor. However, this method has the advantage that high quality images can be obtained through simple dry processing. However, this system has significantly lower photosensitivity than systems using silver halide, and requires a large light source or long exposure time for exposure. "Problems to be Solved by the Invention" The present invention improves the drawbacks of the above techniques. That is, an object of the present invention is to improve the sensitivity of an image recording method using microcapsules containing a photosensitive composition to the same level as a system using silver halide, use a small light source, and short exposure time. The goal is to make recording possible. "Means for Solving the Problems" The object of the present invention is to coat a support with at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image forming substance. Silver halide, the polymerizable compound, and the color image-forming substance are encapsulated in the same microcapsules, and a photosensitive composition is imagewise exposed to form a latent image, which is then heated to form a latent image. After curing the microcapsules by polymerizing the polymerizable compound in the existing areas to produce a high molecular compound, the microcapsules are overlapped with an image-receiving material to which the color image-forming substance can be transferred and pressurized to remove the areas where no latent image exists. This is accomplished by an image recording method comprising rupturing at least a portion of the microcapsules to transfer the color image-forming substance to the image-receiving material. The recording material used in the present invention uses a photosensitive silver halide as an optical sensor, and the latent image nuclei of the silver halide generated by exposure act as a catalyst to cause an oxidation-reduction reaction between the silver salt and the reducing agent, and the process The microcapsules are cured by performing a polymerization reaction of the polymerizable compound contained in the microcapsules using the radical intermediate produced in the above as an initiator to generate a polymer compound. Conventionally, there is a detailed description, for example, in Japanese Patent Publication No. 47-20741, regarding a method of producing a polymer compound imagewise by utilizing the high photosensitivity of photosensitive silver halide, but this method is based on a wet development process. was necessary. A major feature of the present invention is that a radical intermediate is generated by a reaction between a silver salt and a reducing agent in a dry system that does not use a developer. In the present invention, depending on the type of photosensitive silver halide used, it is possible to cure the microcapsules in both exposed and unexposed areas. Therefore, both negative and positive images can be freely created with respect to the original image, and in some cases, both negative and positive images can be created at the same time. for example,
When obtaining a color image by transferring the contents of uncured microcapsules, a normal negative silver halide emulsion can be used to obtain a positive image relative to the original image; In order to form a
3,367,778, 3,447,927, and mixtures of surface-imaged silver halide emulsions and internal-imaged silver halide emulsions as described in U.S. Pat. No. 2,996,382. I can do it. Silver halides that can be used in the present invention include silver chloride,
Silver bromide, silver iodide, or silver chlorobromide, silver chloroiodide,
Either silver iodobromide or silver chloroiodobromide may be used. The halogen composition within the particles may be uniform. It may be a multiple structure with different compositions on the surface and inside (Japanese Patent Application Laid-open Nos. 57-154232, 58-108533, 59-48755).
No. 59-52237, U.S. Pat. No. 4,433,048 and
EP100984). In addition, tabular grains with a grain thickness of 0.5 microns or less, a grain size of at least 0.6 microns, and an average aspect ratio of 5 or more (U.S. Pat. No. 4,414,310)
No. 4435499 and OLS3241646A ₁ , etc.) or monodisperse emulsions with a nearly uniform particle size distribution (Japanese Patent Application Laid-Open No. 178235, No. 58-100846, No. 58-1008).
14829, WO83/02338A ₁ , EP64412A ₃ and EP 83377A ₁ ) can also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes. The average grain size of the silver halide used in the present invention is preferably from 0.001 micron to 10 microns, more preferably from 0.001 micron to 5 microns. These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method, and the reaction method of soluble silver salt and soluble halide salt may be one-sided mixing method, simultaneous mixing method, or these methods. Any combination is acceptable. A back-mixing method in which particles are formed in an excess of silver ions or a controlled double-jet method in which pAg is kept constant can also be used. Furthermore, in order to accelerate grain growth, the concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Laid-Open No. 55-142329
No. 55-158124, U.S. Patent No. 3650757, etc.). Epitaxial junction type silver halide grains can also be used (Japanese Patent Application Laid-Open No. 16124/1984, US Pat. No. 4,094,684). When silver halide is used alone without an organic silver salt oxidizing agent in the present invention, it is preferable to use silver chloriodide in which an X-ray pattern of silver iodide crystals can be observed.
Silver iodobromide and silver chloroiobromide. For example, silver bromide particles are prepared by adding a silver nitrate solution to a potassium bromide solution, and then potassium iodide is added to obtain silver iodobromide having the above-mentioned properties. In the step of forming silver halide grains used in the present invention, ammonia,
Organic thioether derivatives described in Japanese Patent Publication No. 47-11386 or sulfur-containing compounds described in Japanese Patent Publication No. 53-144319 can be used. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present. Further, for the purpose of improving high illuminance failure and low illuminance failure, water-soluble iridium salts such as iridium chloride (2) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used. The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening, and therefore the Nudel water washing method or the precipitation method can be applied. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-126526).
No. 215644). The silver halide emulsion of the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains.
It is also possible to use a direct reversal emulsion, which is a combination of an internal latent image type emulsion and a nucleating agent. Internal latent image emulsions that have achieved this purpose are disclosed in US Pat. No. 2592250 and US Pat.
No. 58-3534 and Japanese Patent Application Laid-open No. 57-136641. Preferred nucleating agents for combination are U.S. Pat.
No. 4255511, No. 4266013, No. 4276364 and
Described in OLS2635316. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m ² in terms of silver. In the present invention, an organic silver salt relatively safe to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic silver salt need to be in contact or at a close distance. Preferably above 80℃
When heated to a temperature of 100° C. or higher, the organometallic oxidizing agent is thought to participate in redox using the silver halide latent image as a catalyst. Examples of organic compounds that can be used to form such an organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. can be mentioned. Silver salts of aliphatic carboxylic acids include behenic acid,
Stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, linolenic acid, oleic acid, adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid , or silver salts derived from camphoric acid. Silver salts derived from fatty acid carboxylic acids having halogen atoms or hydroxyl groups or thioether groups of these fatty acids can also be used. Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3,5
-dihydroxybenzoic acid, o-, m- or p
-methylbenzoic acid, 2,4-dichlorobenzoic acid,
acetamidobenzoic acid, p-phenylbenzoic acid,
Representative examples include silver salts derived from gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid, or 3-carboxymethyl-4-methyl-4-thiazoline-2-thione. Silver salts of compounds having mercapto or thiocarbonyl groups include 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-
Aminothiadiazole, 2-mercaptobenzthiazole, S-alkylthioglycolic acid (alkyl group having 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl -Silver derived from mercapto compounds such as those described in U.S. Pat. No. 4,123,274, such as -4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole, or 3-amino-5-benzylthio-1,2,4-triazole. Salt is an example. Silver salts of compounds having an imino group include benzotriazoles and their derivatives described in Japanese Patent Publication No. 44-30270 or 45-18416, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, and 5-chlorobenzotriazole. halogen-substituted benzotriazoles, butycarboimidobenzotriazole, etc., carbimidobenzotriazoles, etc., JP-A-58
-Nitrobenzotriazoles described in No. 118639,
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole described in JP-A-58-118638, etc.
Typical examples include silver salts derived from 1,2,4-triazole, 1H-tetrazole, carbazole, sacchulin, imidazole and derivatives thereof, etc., as described in US Pat. No. 4,220,709. In addition, organic metal salts other than silver salts such as silver salts and copper stearate described in RD17029 (June 1978), and carboxylic acids having alkynyl groups such as phenylpropiolic acid described in Japanese Patent Application No. 58-221535. Silver salts can also be used in the present invention. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 1mg to 10g/
^m2 is appropriate. The silver halide used in the present invention may be spectrally sensitized with dyes. The dyes used include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Holopolar cyanine dye, hemicyanine dye,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes as a basic heterocyclic nucleus can be applied to 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.; nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus , indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable.
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.,
Nos. 2933390 and 36357210), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 374351), 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. The reducing agent that can be used in the present invention is
Compounds described in No. 20741, such as resorcinols, m-aminophenols, m-phenylenediamines, 5-pyrazolones, alkylphenols, alkoxyphenols, naphthols, aminonaphthols, naphthalene diols, Alkoxynaphthols, hydrazines, etc. can be used. Specific examples of these include resorcin, 2-methylresorcin, orcine, phloroglucin, phloroglucin monomethyl ether, phloroglucin dimethyl ether, m-aminophenol, m-
Dimethylaminophenol, m-diethylaminophenol, N,N-dimethyl-m-phenylenediamine, N,N-diethyl-m-phenylenediamine, 3-methyl-5-pyrazolone, 3,4-
Dimethyl-5-pyrazolone, 1,3-dimethyl-
5-pyrazolone, 1-phenyl-3-methyl-5
-Pyrazolone, P-ethylphenol, P-dodecylphenol, P-methoxyphenol, P-
Benzyloxyphenol, P-hydroxydiphonyl ether, 4-methyl-1-naphthol,
2-methyl-1-naphthol, 1-methyl-2-
naphthol, 6-amino-1-naphthol, 8-
Amino-2-naphthol, 1,3-dihydroxynaphthalene, 4-methoxy-1-naphthol, O
-Tolylhydrazine hydrochloride, P-tolylhydrazine hydrochloride, acetohydrazide, benzhydrazide, toluenesulfonylhydrazine, N,N'-
Examples include diacetylhydrazine. Two or more types of these reducing agents can be used in combination if necessary. Further, the above-mentioned reducing agents and conventional photographic reducing agents such as hydroquinone, catechol, P-substituted aminophenols, P-phenylenediamines, 3-pyrazolidones, etc. can also be used together. The amount of reducing agent added can vary widely, but generally it is 0.1 to 1500% of the silver salt.
mol %, preferably 10 to 300 mol %. Examples of the polymerizable compound that can be used in the present invention include addition polymerizable monomers, oligomers, and polymers thereof. As addition polymerizable monomers, compounds having one or more carbon-carbon unsaturated bonds can be used. Examples of these are acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, and styrenes. , vinyl ethers, vinyl esters, N-vinyl heterocycles, and derivatives thereof. Further, in order to increase the S/N ratio of the obtained color image, it is desirable to use a crosslinkable compound having an effect of increasing the viscosity or degree of curing of the produced polymer compound. The crosslinkable compound referred to here is one that has multiple vinyl groups or vinylidene groups in its molecule.
It is a so-called polyfunctional monomer. Preferred examples of the polymerizable compound used in the present invention are shown below. Acrylic acid, methacrylic acid, butyl acrylate, tomexyethyl acrylate, butyl methacrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N
-Acryloylmorpholine, N-acryloylpiperidine, glycidyl acrylate, 2-ethylhexyl acrylate, acrylic acid anilide, methacrylic acid anilide, styrene, vinyltoluene, chlorostyrene, methoxystyrene, chloromethylstyrene, 1-vinyl-2-methylimidazole, 1 -vinyl-2-undecylimidazole, 1-vinyl-2-andecylimidazoline,
N-vinylpyrrolidone, N-vinylcarbazole, vinylbenzyl ether, vinylphenyl ether, methylene-bis-acrylamide, trimethylene-bis-acrylamide, hexamethylene-bis-acrylamide, N,N'-diacryloylpiperazine, m-phenylene -Bis-acrylamide, P-phenylene-bis-acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, bis(4-acryloxypolyethoxyphenyl)propane, 1,5-pentanedio- polyacrylate, neopentyl glycol diacrylate, 1,6-hexanediol acrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetraacrylate, N-
Methyloacrylamide, diacetone acrylamide, triethylene glycol dimethacrylate. Also, a condensate of a polymer compound having a vinyl group or a vinylidene group, such as a polymer compound having a hydroxyl group, an amino group, an epoxy group, a halogen atom, or a sulfonyloxy group in the side chain, and acrylic acid or methacrylic acid, etc. can also be used in the present invention. Furthermore, compounds in which a vinyl salt or a vinylidene group is bonded to the core of the reducing agent described above, such as m-N, N
-di(acryloyloxyethyl)aminophenol, P-acryloyloxyethoxyphenol, etc. can also be used as the polymerizable compound, and in this case, the reducing agent and the polymerizable compound can be used both. Furthermore, a compound containing a vinyl group in the molecule of a color image-forming substance, such as a dye or a leuco dye, can also be used as a polymerizable compound, and in this case can serve both as a polymerizable compound and a color image-forming substance. The polymerizable compound of the present invention is 0.05 to 1200% by weight, preferably 5 to 1200% by weight, based on the silver halide salt.
950% by weight can be used. There are a variety of color image-forming materials that can be used in the present invention. For example, dyes and pigments are examples of substances that are themselves colored. When these are used, a color image can be formed by rupturing the uncured microcapsules under pressure and transferring the dye or pigment to the image-receiving material using an appropriate method. In addition to commercially available dyes and pigments, there are also known dyes and pigments described in various documents (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1972; "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1978). things are available. These dyes or pigments are used after being dissolved or dispersed. On the other hand, uncolored color image-forming substances include those that are colorless or pale in themselves but develop color when subjected to some kind of energy such as heating, pressure, or light irradiation; It is classified as one that develops color when it comes into contact with another component. Examples of the former include thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of these develop color upon heating, pressurization, light irradiation, or air oxidation. Examples of the latter include various systems that develop color through acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. For example, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols; aromatic diazonium salts, diazotates, Systems that utilize azo coupling reactions between diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine, ferric ions, and gallic acid, and reactions between phenolphtylenes and alkaline earth complexes. Chelate formation reactions such as reactions with similar metal ions; stearic acid secondary
Redox reactions such as the reaction between iron and pyrogallol and the reaction between silver behenate and 4-methoxy-1-naphthol can be used. Furthermore, as another example of a system in which color is developed 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 mixture at the same time that the two components are mixed by breaking the microcapsules during pressurization or immediately after pressurization. Color formers in the color former/developer system include (1) triarylmethane, (2) diphenylmethane, (3) xanthene, (4) thiazine, and (5) spiropyran compounds. For example,
Examples include those described in JP-A No. 55-27253. Among them, (1) triarylmethane type, (3)
Xanthene-based coloring agents are preferred because they often cause less fog and provide high coloring density. Specific examples include crystal violet lactone, 3-diethylamino-6-chloro-7-(β-ethoxyethylamino)fluoran, 3-diethylamino-
6-Methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3-dichlorohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7 -o-chloroanilinofluorane, etc., and these can be used alone or in combination. As the color developer, phenolic compounds, organic acids or metal salts thereof, oxybenzoic acid ester acid clay, etc. are used. Examples of phenolic compounds include 4,4'-isopropylidene-diphenol (bisphenol A), p-tert-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, and 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, p-phenylphenol-formalin condensate, and the like. Examples of organic acids or metal salts thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, o-toluic acid, p-toluic acid, salicylic acid, 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 its zinc, lead, aluminum, magnesium, and nickel salts are useful. In particular, salicylic acid derivatives and their zinc salts or aluminum salts are excellent in terms of color developing ability, fastness of colored images, and storage stability of recording sheets. As the oxybenzoic acid ester, ethyl p-oxybenzoate, butyl p-oxybenzoate, p-oxybenzoate,
-heptyl oxybenzoate, benzyl p-oxybenzoate, etc. These color developers can be added as a eutectic with a thermofusible substance with a low melting point, or a low melting point compound can be added to the surface of the color developer particles in order to melt at a desired temperature and cause a color reaction. It is preferable to add it in a fused state. Specific examples of low melting point compounds include higher fatty acid amides such as stearamide, erucic acid amide, palmitic acid amide, ethylene bisstearamide, waxes such as higher fatty acid esters, phenyl benzoate derivatives, and urea derivatives. Yes, but not limited to this. Other color formers/developer systems include, for example, phenolphthalein, fluorescein, 2',4',5',7'-tetrabromo-3,4,5,
Examples include 6-tetrachlorofluorescein, tetrabromophenol blue, 4,5,6,7-tetrabromophenolphthalein, eosin, aurin cresol red, and 2-naphtholphenolphthalein. Color developers include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, and triazoles. Examples include nitrogen-containing compounds such as monophorins, piperidines, amidines, formazines, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenyl imidazole, 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,-dicyclohexylguanidine, 1,2-dicyclohexyl-3-
Phenylguanidine, 1,2,3-tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, There is 2-benzoylhydrazinobenzothiazole. The color image forming substance (or color former) of the present invention is used in an amount of 0.5 to 20 parts by weight, particularly preferably 2 to 7 parts by weight, based on 100 parts by weight of the polymerizable compound.
The color developer is used in an amount of about 0.3 to 80 parts by weight per 1 part by weight of the color former. Furthermore, storage stability can be improved by encapsulating a thermal polymerization inhibitor in microcapsules. The amount of the thermal polymerization inhibitor added is preferably 0.1 to 10 mol% relative to the polymerizable compound. When the color image forming material used in the present invention utilizes a reaction between two or more components, it is desirable that each component exists separately. For example, one component is contained in microcapsules and the other component is contained in an image-receiving material, and the uncured microcapsules rupture when pressurized, the contents are transferred to the image-receiving material, and the two come into contact. Preferred are methods that form color images. In addition, when obtaining a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan in the subtractive color method, at least three types of halogenated materials sensitive to different spectral regions must be used. It is necessary to have a silver emulsion. Typical combinations of at least three light-sensitive silver halide emulsions sensitive to different spectral regions include a combination of a blue-sensitive emulsion, a green-sensitive emulsion and a red-sensitive emulsion, a green-sensitive emulsion, a red-sensitive emulsion and an infrared-sensitive emulsion. Combination of light-sensitive emulsions, blue-sensitive emulsions,
Examples include a combination of a green-sensitive emulsion and an infrared-sensitive emulsion, a blue-sensitive emulsion, a red-sensitive emulsion, and an infrared-sensitive emulsion. Note that the infrared light-sensitive emulsion herein refers to an emulsion that is sensitive to light of 700 nm or more, particularly 740 nm or more. For example, when using a combination of a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion, the blue-sensitive microcapsules contain a yellow imaging substance;
It is sufficient that the green-sensitive microcapsules contain a magenta image-forming substance and the red-sensitive microcapsules contain a cyan image-forming substance. In the present invention, various promoters can be used to promote the reaction between the silver salt and the reducing agent.
The accelerator includes a compound that makes the reaction system basic and accelerates development, and this includes a base or a base precursor. Various bases or base precursors are known. The base precursor referred to here is one that releases a base component upon heating, and the base component released may be an inorganic base or an organic base. Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates; ammonium aqueous bases as inorganic bases; Oxides; hydroxides of quaternary alkylammonium; hydroxides of other metals, etc., and organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamino)
phenyl]methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 8 or more are particularly preferred. Examples of base precursors include salts of organic acids and bases that decarboxylate and decompose when heated, compounds that decompose and release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothsen rearrangement, and Beckman rearrangement. Compounds that release a base upon reaction and compounds that generate a base by electrolysis or the like are preferably used. Preferred base precursors of the former type that generate a base upon heating include trichloroacetic acid salts described in British Patent No. 998949, etc., α-sulfonylacetic acid salts described in U.S. Patent No. 4060420, and JP-A-59-180537. 2-carboxycarboxamide derivatives described in U.S. Pat. 1977-
No. 195237), patent application using Lothsen rearrangement (1982)
Hydroxam carbamates as described in No. 43860,
JP-A-59-157637 that produces nitrile by heating
Examples include aldoxime carbamates described in No. In addition, British Patent No. 998945, U.S. Patent No. 3220846, Japanese Patent Application Publication No. 1983-22625, 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. Moreover, these bases or base precursors can be used in a wide range of ways. A useful range is 50% by weight or less, more preferably 0.01% to 40% by weight of the photosensitive material after coating and drying. In the present invention, it is important that at least the polymerizable compound and the color image forming substance among these components are encapsulated in the same microcapsule. Furthermore, other additives such as a salt precursor may also be encapsulated in the same microcapsules as described above, if necessary. It is desirable to use a solvent together during encapsulation. As the solvent, in addition to the above-mentioned organic solvents, phenyl alkanes, chlorinated paraffin, etc. are preferable. In this case, it is preferable that the polymerizable compound is included in the capsule in an amount of about 5 to 95% by weight, and the color image forming substance is included in the capsule in an amount of about 0.1 to 15% by weight. The capsule wall is preferably made of gelatin coacervation, polyurea, polyurethane, polyester, thermosetting polymer, or a mixture thereof. In particular, by using a polymer precipitation method or an encapsulation method by reactant polymerization from inside an oil droplet, capsules with uniform particle size, dense walls, and excellent storage stability can be obtained. A specific example of encapsulation is provided in U.S. Patent No.
It is described in detail in the specifications of No. 3726804 and No. 3796669. The particle size of the capsules is preferably 80μ or less, particularly 30μ or less from the viewpoint of ease of handling during storage. In addition, from the viewpoint of ease of pressurization, it is desirable that the thickness be 0.1μ or more. That is, it is desirable that the capsules are substantially not deformed at pressures of about 10 kg/cm ² or less, and about 50% of the capsules are destroyed at pressures of about 50 kg/cm ² . When coating capsules and the like on supports, protective agents such as binder starches such as PVA or latex are used. In addition, various additives, binders, antioxidants, anti-smearing agents, surfactants, coating methods, usage methods, etc. used in recording systems are well known, and are disclosed in U.S. Pat. patent
1232347, JP-A No. 50-44012, JP-A No. 50-50112,
No. 50-127718, No. 50-30615, US Patent
There are disclosures in No. 3836383, No. 3846331, etc., and those methods can be used. When the other coloring component not contained in the microcapsules is included in the image-receiving material, it is dispersed in a binder such as PVA or latex and applied. In this case, the above-mentioned protective agents, antioxidants, anti-smudge agents, surfactants, etc. can be used in addition to the color-forming components. The supports used in the light-sensitive material and image-receiving material in the present invention are those that can withstand processing temperatures. Common supports include glass,
Paper, metals and analogs thereof are used, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. The photosensitive material of the present invention may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a peeling layer, and a matting agent layer, if necessary. In particular, the protective layer preferably contains an organic or inorganic matting agent for the purpose of preventing adhesion. In addition, light-sensitive materials and image-receiving materials may contain antifoggants, fluorescent brighteners, anti-fading agents, anti-halation and anti-irradiation dyes, pigments (including white pigments such as titanium oxide), water release agents, heat It may also contain a polymerization inhibitor, a surfactant, a vinyl compound dispersed in a heat solvent, and the like. Various exposure means can be used in the present invention. The latent image is obtained by screen exposure to radiation, including visible light. In general, commonly used light sources such as sunlight, strobes, flashlights, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams,
Also, CRT light sources, plasma light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources.
It is also possible to use an exposure means that combines a microshutter array using an LCD (liquid crystal) or PLZT (lanthanum-doped lead titanium zirconate) with a linear light source or a planar light source.
The type of light source and the amount of exposure can be selected depending on the wavelength to which silver halide is sensitive by dye sensitization and the sensitivity. The original image used in the present invention may be a black and white image or a color image. The original image may be a line image such as a drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original may be carried out by contact printing over the original, reflection printing, or enlargement printing. In addition, images taken with video cameras and image information sent from television stations can be directly processed.
It is also possible to output the image to a CRT or FOT, form the image on a photosensitive material using a contact lens or a lens, and then print it. Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. this
It is difficult to create an LED that effectively emits blue light. In this case, to reproduce a color image, three LEDs that emit green, red, and infrared light must be used.
The seeds may be designed so that the emulsion portions sensitive to these lights each contain yellow, magenta, and cyan image-forming substances. That is, the green-sensitive area may contain a yellow image-forming substance, the red-sensitive area may contain a magenta image-forming substance, and the infrared-sensitive area may contain a cyan image-forming substance. Other combinations are also possible as required. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light-receiving element such as a CCD and storing it in the memory of a computer, processing this information as necessary and performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source. There is also a method of directly emitting light from three types of LEDs for exposure based on the processed information. These exposure amounts vary depending on the type of silver halide used and the degree of sensitization. In the present invention, a conventionally known method can be used as a heating method after imagewise exposure. for example,
The photosensitive material may be brought into direct contact with a hot plate such as a hot plate or a drum, or may be transported using a heat roller. Heating can also be performed using air heated to a high temperature, high frequency heating, or a laser beam. Depending on the photosensitive material, it can also be heated using an infrared heater. Furthermore, a method of heating using overcurrent generated by electromagnetic induction can also be applied. Alternatively, a liquid inert to the photosensitive material, such as a fluorine-based liquid, may be heated in a heated bath. Furthermore, the photosensitive material may be heated by providing a heat source separate from the heating means described above. for example,
It is also possible to provide a layer of conductive particles such as carbon black or graphite in a photosensitive material and utilize the Joule heat generated when electricity is applied. The heating temperature at this time is generally 80℃~200℃, preferably 100℃~
The temperature is 160℃. Various patterns can be applied as the pattern for heating the photosensitive material. The most common method is heating at a constant temperature, but depending on the characteristics of the photosensitive material, multi-stage heating, such as heating at high temperature for a short time and then gradually lowering the temperature, is effective. The heating time in this case is generally 2 seconds to 5 minutes, preferably 5 minutes.
It is from seconds to one minute. If the photosensitive material is susceptible to air oxidation during heating, it is effective to deaerate the area around the heating section or replace the area with an inert gas. Further, the surface of the photosensitive material may be brought into direct contact with a heated portion or may be exposed to air. When developing with the surface of the photosensitive material facing the air, it is also effective to attach a cover to prevent moisture and volatile components from evaporating from the photosensitive material and to keep the material warm. Example 1 [Preparation of photosensitive silver halide emulsion] (Emulsion) The following solution was prepared. (Solution A) 100 ml of isopropyl alcohol was added to and dissolved in 13 g of benzotriazole and 3 g of polyvinyl butyral. (Solution B) Add water to 17g of silver nitrate and dissolve it,
ml. (Solution C) Water was added to dissolve 2.38 g of potassium bromide and 0.17 g of potassium iodide to make 50 ml. Solution A was placed in a reaction vessel, and solution B was added thereto over 5 minutes at 40° C. with sufficient stirring. After 5 minutes had passed after this addition was completed, solution C was further added over a period of 5 minutes. After this addition was completed, stirring was continued for 5 minutes,
This liquid was filtered, 200 ml of a 20% isopropyl solution of polyvinyl butyral was added to this liquid, and the mixture was stirred for 20 minutes using a homogenizer to obtain Emulsion 1. The yield of this emulsion was 250 g. (Emulsion) The following solution was prepared. (Solution A) 200 ml of isopropyl alcohol was added to 3 g of polyvinyl butyral and dissolved. (Solution B) Add water to 17g of silver nitrate and dissolve it to 20ml.
And so. (Solution C) Water was added to dissolve 11.9 g of potassium bromide and 0.83 g of potassium iodide to make 50 ml. Solution A was placed in a reaction container, and solutions B and C were simultaneously added to solution A over 10 minutes at 40° C. while stirring well. Five minutes after the addition was completed, the liquid was filtered, and then 200 ml of a 20% isopropyl alcohol solution of polyvinyl butyral was added thereto and dispersed using a homogenizer for 20 minutes to form an emulsion. The yield of this emulsion was 250 g. (Emulsion) The following solution was prepared. (Solution A) Gelatin 12g, sodium chloride 5.6
g and potassium bromide 0.6g in 1000ml water
dissolved in (Solution B) 100 g of silver nitrate was dissolved in water to make 300 ml. (Solution C) 40 g of sodium chloride and 20 g of potassium bromide were dissolved in water to make 300 ml. Solution A was placed in a reaction vessel, and while maintaining the temperature at 50°C, solutions B and C were simultaneously added into solution A over 90 minutes. After removing excess salt from the produced silver chlorobromide emulsion using a well-known method, 70 g of water was added to adjust the pH to 6.0, and gold sensitization and sulfur sensitization were performed to obtain a silver chlorobromide emulsion (yield 400 g). ) was obtained. (Emulsion) The following solution was prepared. (Emulsion A) Gelatin 10g, sodium chloride 3g
was dissolved in 1000ml of water. (Emulsion B) 100 g of silver nitrate was dissolved in water to make 600 ml. (Emulsion C) 6 g of sodium chloride and 56 g of potassium bromide were dissolved in water to make 600 ml. Solution A was placed in a reaction vessel, and while maintaining the temperature at 75°C, solutions B and C were simultaneously added into solution A over a period of 40 minutes. Average particle size thus prepared
A 0.35μ monodisperse cubic silver chlorobromide emulsion was washed with water, desalted, and then treated with sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
Chemical sensitization was performed. The yield of emulsion was 600g. (Emulsion) Solution D in which 160 mg of the following dye was dissolved in 400 ml of methanol An emulsion with a dye adsorbed thereon was prepared in the same manner as the emulsion, except that it was added to solution A for 40 minutes simultaneously with the addition of solutions B and C of the emulsion. (Emulsion) Solution E in which 160 mg of the following dye was dissolved in 400 ml of methanol An emulsion with a dye adsorbed thereon was prepared in the same manner as the emulsion, except that it was added to solution A for 40 minutes simultaneously with the addition of solutions B and C of the emulsion. [Preparation of microcapsules] 28 g of trimethylolpropane triacrylate
0.7 g of N-phenylglycine as component (c) shown in Table 1 was added to a monomer mixture of 7 g of methyl methacrylate and dissolved using an ultrasonic disperser. On the other hand, 6 g of methylene chloride, 0.7 g of components (a) and 2.1 g of (b) shown in Table 1, and 3-dimethylamino-6-chloro-7-anilinofluorane as a coloring agent.
2.1g was dissolved and added to the previous solution to form an oil phase. Separately, for comparison, one without component (c), one in which 3.5 g of benzoin butyl ether was used instead of components (a), (b), and (c) and dissolved in the monomer mixture, and component (a) , (b) and (c), emulsions () to () and component (d) were mixed in the proportions shown in Table 1. Meanwhile, 17.5 g of 10% gum arabic aqueous solution, 18.8 g of 12% isobutylene/maleic anhydride aqueous solution, distilled water
26.8 g of the mixture was adjusted to pH 3.5 with sulfuric acid, 4.6 g of urea and 0.6 g of resorcin were added, and the monomer mixture was emulsified and dispersed in this solution to give a concentration of 3μ.
Next, add 12.9 g of 36% formalin and mix to 60
The temperature was raised to .degree. C., and after 1 hour, 9.0 g of 5% ammonium sulfate aqueous solution was added, and the mixture was further stirred for 1 hour while maintaining the temperature at 60.degree. C., and then cooled. Thereafter, the pH was adjusted to 9.0 with NaOH. [Preparation of photosensitive sheet and image-receiving sheet] Add 1.53 g of a 15% polyvinyl alcohol aqueous solution and 3.47 g of distilled water to 5 g of the capsule liquid thus obtained.
g and 0.57 g of starch were added to prepare a coating solution. This was coated on art paper using coating rod 10 and dried at 50°C for 15 minutes to obtain photosensitive sheets 1 to 5. Meanwhile, 0.6 g of 48% SBR latex in 21.8 g of water,
4g of 10% etherified starch aqueous solution, zinc carbonate
Add 2.1g of sodium silicate, 1.3g of 50% aqueous solution of sodium silicate, 0.1g of sodium hexametaphosphate, and 13g of acid clay.
The mixture was stirred with a homogenizer for 15 minutes. This was applied to art paper using Coating Rod 18 and dried at 100°C for 2 minutes to obtain an image-receiving sheet. [Image reproduction and results] Image reproduction was performed as follows. 350 ~ obtained by passing a line drawing original onto the above-mentioned photosensitive sheet and passing it through a bandpass filter from an ultra-high pressure mercury lamp.
Light with a wavelength of 500 nm was irradiated. After exposure, photosensitive sheets No. 3, 4, and 5 are heated at 120° C. for 30 seconds. The exposed photosensitive sheet and image receiving sheet were stacked so that their coated surfaces faced each other, and a linear pressure of 100 kg/cm was applied.
was passed through a pressure roller. The capsules in the unexposed areas were destroyed and transferred to the image receiving sheet. The transferred area gave a clear black image with a density of 1.0. The density of the part corresponding to the exposed area changes depending on the exposure amount, but the sensitivity (equivalent to foot sensitivity) was defined as the lowest exposure amount that resulted in a density of 0.1 or less. In other words, the smaller the exposure energy, the higher the sensitivity.
The results are shown in Table 1.

[Table] As can be seen from the results in Table 1, the sensitivity of the photosensitive sheets of the present invention (Nos. 3, 4, and 5) significantly increased compared to cases in which no silver halide emulsion was used (Comparative Examples 1 and 2). Can be seen. Example 2 In the preparation example of microcapsules in Example 1, silver halide emulsion () or () or () was used instead of components (a), (b), and (c), and the color former 3-diethylamino Three capsule solutions (α), (β), and (γ) Prepare.

[Table] 5 g of each of the capsule liquids thus obtained were mixed, and 1.53 g of a 15% polyvinyl alcohol aqueous solution, 3.47 g of distilled water, and 0.57 g of starch were added to prepare a coating liquid.
This was applied to art paper using coating rod 20 and dried at 50°C for 15 minutes to obtain a photosensitive sheet. After exposing the photosensitive sheet thus obtained to the light shown in Table 3, it was heated at 120°C for 30 seconds, and the exposed photosensitive sheet and the image receiving sheet prepared in the same manner as in Example 1 were placed so that the coated surfaces faced each other. Stack them like this and apply a linear pressure of 100
It was passed through a pressure roller of Kg/cm. The capsules in the unexposed areas were destroyed, and the image-receiving sheet developed colors as shown in Table 3.

[Table] Furthermore, if the photosensitive sheet of the present invention is exposed to light through a transparent positive image such as a commonly used slide, and then heated and pressurized in the same manner, a positive image can be obtained on the image-receiving sheet. can.

Claims (1)

[Claims] 1 At least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image forming substance are coated on a support, and at least the photosensitive silver halide, the polymerizable compound, and the color image forming substance are coated on a support. The photosensitive composition encapsulated in the same microcapsules is imagewise exposed to form a latent image, and then heated to polymerize the polymerizable compound in the area where the latent image exists to form a polymer compound. After curing the microcapsules, they are stacked with an image-receiving material to which the color image-forming substance can be transferred and pressurized to rupture at least a portion of the microcapsules in areas where no latent image exists, thereby forming the color image-forming substance. An image recording method comprising transferring an image forming substance to the image receiving material.