JPH0422507B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to photosensitive materials. More specifically, photosensitive silver halide is used as an optical sensor,
The present invention relates to a photosensitive material that utilizes an image-like latent image formed on silver halide during irradiation with actinic radiation to form a polymer compound by heating or uniform exposure, thereby immobilizing coexisting dyes or dye-forming substances. "Prior Art" Various recording materials using microcapsules are known. For example,
No. 14344 (U.S. Pat. No. 3,219,446) involves imagewise exposure of a sensitive sheet having many fluid droplets that become non-flowing when exposed to light, superimposing this onto a receiver sheet and applying pressure across the sheet. By adding
A method for transferring an image according to exposure onto this image-receiving sheet is disclosed. Also, JP-A-52-89915
In this issue, one component of a two-component heat-sensitive color-forming material and a photopolymerizable monomer are encapsulated in microcapsules, the other component of the heat-sensitive color-forming material, and the microcapsules are mixed and coated on a base sheet, and this photosensitive sheet is produced. A method is disclosed in which an image is obtained by exposing the microcapsules in an imagewise manner to harden the microcapsules in the exposed areas, and then heating the entire surface so that only the unexposed areas develop color.
Further, JP-A-57-124343, JP-A-57-179836, and JP-A-57-197538 describe an image forming method using microcapsules containing a vinyl compound, a photopolymerization initiator, and a dye precursor, in which pressure is applied to the entire surface after exposure. A method of forming a dye image that does not require heating by adding a dye is disclosed. Also, special public service 54-20852
(U.S. Pat. No. 3,700,439) discloses an imaging method utilizing encapsulated Michler's ketone as a photosensitive material. Also US Patent 3072481
No. 1 is a method of encapsulating a light-sensitive substance that readily converts to a colored form in a liquid but is light-insensitive when in solid form, imagewise exposing a layer of this encapsulation to light, and then rupturing the capsule. A method of forming an image by evaporating a solvent, a so-called photosensitive and pressure sensitive image forming method is disclosed. Various image forming methods using the above-mentioned microcapsules are known, but all of them have in common a low sensitivity to light, particularly a marked lack of sensitivity to green light and red light. In addition, an attempt to increase this sensitivity has the disadvantage that storage stability decreases. On the other hand, various image forming methods using silver halide as a photosensor other than so-called conventional photographic materials are known. For example, British Patent No. 866631 discloses a method for directly causing photopolymerization using silver halide as a catalyst. However, it has not been possible to obtain as high a sensitivity as when silver halide is reduced by ordinary development. Furthermore, Belgian Patent No. 642477 discloses that exposed silver halide grains are developed with an ordinary developer, and then the resulting silver image or unreacted silver halide is used as a catalyst to cause polymerization, thereby forming a polymer compound into an image. Although a method for forming the same is disclosed, this requires complicated operations. Furthermore, Special Publication No. 11149, No. 45-11149, No. 47-
No. 20741, No. 49-10697, No. 57-138632, No. 58
-169143 describes that when exposed silver halide is developed using a reducing agent, the reducing agent is oxidized and at the same time, coexisting vinyl compounds start polymerizing to form an image-like polymeric substance. Although a method is disclosed, this method requires a liquid development step. There are various known image forming methods using silver halide as a photosensor, but all of them have drawbacks such as not being able to obtain high sensitivity or requiring complicated development processing steps. ing. In contrast, Japanese Patent Application No. 59-191353 proposes a simple image forming method using heat development. "Problems to be Solved by the Invention" The present invention has (1) high sensitivity to light (sensitivity to green light and red light as necessary), (2) excellent stability over time, and (3) simple and convenient construction. An object of the present invention is to provide a photosensitive material that enables image formation by manipulation. "Means for Solving the Problems" The present invention provides at least a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image forming substance on a support, and at least a photosensitive silver halide among them. This is a photosensitive material characterized in that silver, a polymerizable compound, and a color image forming substance are encapsulated in the same microcapsule. The recording material used in the present invention uses photosensitive silver halide as a photosensor, and latent image nuclei of silver halide generated by exposure act as a catalyst to cause an oxidation-reduction reaction between the silver salt and the reducing agent, and in the process, A polymerization reaction is carried out using the resulting radical intermediate as an initiator, or a radical produced by reacting this product with another compound after a redox reaction between a reducing agent and a silver salt is used as an initiator. The polymerization reaction is carried out as follows. It was unexpected from conventional knowledge that this series of reactions would be significantly accelerated by heating or uniform exposure, and in particular,
It is a completely new finding that a radical intermediate is generated by the 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 react with both exposed and unexposed areas to produce a polymer compound. The areas where polymeric compounds have formed (microcapsules) have increased pressure resistance compared to the areas where polymeric compounds have not formed (microcapsules), and as a result, the areas where polymeric compounds have not formed can be turned into image-receiving materials by applying pressure. By transferring or the like, a color image can be formed using a color image forming substance. Therefore, in the present invention, depending on the type of photosensitive silver halide used or the color image forming process adopted, it is possible to freely create either a negative image or a positive image on the original image, and in some cases, It is also possible to create both negative and positive images at the same time. For example, when obtaining a color image by transferring an area where no polymer compound is formed, a normal negative-working silver halide emulsion can be used to obtain a positive-working image with respect to the original image. To form a negative image, US Pat. No. 2,592,250,
The internal image silver halide emulsions described in US Pat.
Mixtures of surface-imaged silver halide emulsions and internal-imaged silver halide emulsions such as those described in US Pat. No. 2,996,382 can be used. In the present invention, yellow, magenta,
In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of cyan, the light-sensitive material must have at least three types of silver halide emulsions that are sensitive to different spectral regions. 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. By using microcapsules in this way, it is possible to separate yellow, magenta, and cyan image-forming substances and include them in the same photosensitive element, thereby making it possible to form color images with simple operations. . When attempting to form a color image using the above-mentioned known technology, the following problems arise: (1) There is no sensitivity to green light or red light, (2) There is low sensitivity to blue light, (3) There is poor stability over time. The photosensitive material of the present invention solves all of the following disadvantages: 4) requiring complicated operations, and (5) requiring processing steps using liquids. can do.
Therefore, the photosensitive material of the present invention is particularly effective in forming color images. The following examples can be given as configurations of the photosensitive element and image receiving element in the present invention. The photosensitive element referred to here includes a photosensitive silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, and at least the polymerizable compound and the color image-forming substance are encapsulated in the same microcapsule. By image-receiving element is meant an element in which the color image-forming material emitted from the photosensitive element is fixed and in which a color image is formed. The structure of these elements and the method of image formation will be described below, but embodiments using the photosensitive material of the present invention are not limited thereto. (1) Where the color image-forming substance is itself a colored dye or pigment; (a) the light-sensitive element and the image-receiving element are coated on separate supports to form a light-sensitive material and an image-receiving material, respectively; After the material has been imagewise exposed, heated or uniformly exposed, it is pressed together with an image-receiving material to form a color image on the image-receiving material. (b) Coating a photosensitive element on a support, coating a light reflecting layer thereon, and coating an image receiving element thereon. This light-sensitive material is imagewise exposed from the support side, heated or uniformly exposed, and then the color image-forming substance is moved imagewise to the image-receiving element by applying pressure to form a color image on the image-receiving element. (2) A color image-forming substance is colorless or light-colored by itself, but develops color when other energy is applied. The configuration in this case may be the same as (a) and (b) in (1) above, but in either case, a step of applying energy to color the color image forming substance is required. However, if the dark coloring occurs simultaneously during heating, exposure, or pressurization in (1), there is no need to add a special process. (3) A color image-forming substance (called a color former in this case) is colorless or light-colored by itself, but develops color when it comes into contact with another component (called a color developer). (a) In the same manner as (a) of (1) above, if a color developer is contained in the image receiving element, the color image forming substance and the color developer come into contact with each other under pressure, forming a color image. do. (b) In the same manner as (b) of (1) above, if a color developer is contained in the image receiving element, the color image forming substance and the color developer come into contact with each other under pressure, forming a color image. do. (c) There is an embodiment in which the photosensitive element and the image receiving element are coated adjacent to each other on the support, or the components of these two elements are mixed and coated. In either case, when the color developer is used as a component of the image-receiving element, the photosensitive material (which also serves as the image-receiving material) is imagewise exposed and then heated, or uniformly exposed and then pressured to destroy it. A color image forming substance and a color developer catalyze in the vicinity of the microcapsules to form a colored image.
In this case, since the color image forming material in the non-colored portion is substantially colorless, it can be visually seen directly as a color image. 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 illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (,) 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 linear reversal emulsion which is a combination of an internal latent image type emulsion and a nucleating agent. Internal latent image emulsions suitable for this purpose are U.S. 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 stable 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. Examples of the silver salt of a compound having an imino group include benzotriazole or its 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 such as butylcarboimidobenzotriazole, etc., carbimidobenzotriazoles such as butylcarboimidobenzotriazole, JP-A-Sho
Nitrobenzotriazoles described in No. 58-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole described in JP-A-58-118638, and 1,2,4-triazoles described in U.S. Pat. No. 4,220,709. and 1H-tetrazole, carbazole,
Representative examples include silver salts derived from saccharin, imidazole, and derivatives thereof. 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 photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. For example, U.S. Patent No. 3954474, U.S. Patent No. 3982947,
-28660 etc. can be used. In the silver halide emulsion preparation method of the present invention,
Gelatin is advantageously used as protective colloid, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull.Soc.Sci.Phot.
Enzyme-treated gelatin as described in Japan) No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. 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 can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be dispersed alone or in a mixture of solvents such as water, methanol, ethanol, acetone, and methyl cellosolve. It may be dissolved in a solvent and added to the emulsion. Alternatively, they may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol, then dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion. Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. Further, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved. When added to an emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives. It may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 4,225,666. The amount added is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide. The reducing agent that can be used in the present invention is
No. 20741, Special Publication No. 45-11149, No. 49-10697,
Compounds described in No. 57-138632 and No. 58-169143, such as resorcinols, aminophenols, 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-hydroxydiphenyl 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, 0-tolylhydrazine hydrochloride, P-tolylhydrazine hydrochloride, acetohydrazide, benzhydrazide, toluenesulfonylhydrazine, N,
N'-diacetylhydrazine, β-amyl phenylhydrazine, such as β-acetylphenylhydrazine, β-acetyl-P-tolylhydrazine, β
-acetyl-P-methoxyphenylhydrazine,
β-acetyl-P-aminophenylhydrazine,
β-formyl-P-aminophenylhydrazine,
β-formyl-2,4-dimethylphenylhydrazine, β-benzoyl-2,4-dimethoxyphenylhydrazine, β-butyroyl-P-tolylhydrazine, βhybaloyl-P-acetylaminophenylhydrazine, β-propionyl- P-dimethylaminophenylhydrazine, β-ethoxycarbonyl-P-aminophenylhydrazine, β-
Dimethylcarbamoyl-P-benzenesulfonamidoenylhydrazine, β-morpholinocarbonyl-P-aminophenylhydrazine, and the like. Two or more types of these reducing agents can be used in combination if necessary. Further, the above-mentioned reducing agent and conventional photographic developer 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 is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% based on the silver salt.
It is. Examples of the polymerizable compound that can be used in the present invention include addition polymerizable monomers, oligomers, and polymers thereof. As an addition polymerizable monomer, one carbon-carbon unsaturated bond is used.
Compounds having more than 100% 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, aryl ethers, aryl esters, and derivatives thereof. All of these compounds are useful in the present invention, but in the present invention, since a heat development process is performed, compounds that are difficult to volatilize during heating and have a boiling point of 80° C. or higher are preferred. 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, methoxyethyl 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-undecylimidazoline,
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 - diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol acrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetraacrylate, N-
Methylol acrylamide, diacetone acrylamide, triethylene glycol dimethacrylate, pentaerythritol tetraaryl ether. Furthermore, the combination of a polymer compound having a vinyl group or a vinylidene group, for example, a polymer compound having a hydroxyl group, amino group, epoxy group, halogen atom, or sulfonyloxy group in the side chain, with acrylic acid, methacrylic acid, or a derivative thereof. Condensates and the like can also be used in the present invention. Furthermore, compounds in which a vinyl group or a vinylidene group is bonded to the core of the reducing agent, 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. 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 using these, a color image can be formed by destroying the portions (microcapsules) in which no polymer is formed and transferring them to an image-receiving material using an appropriate method. In addition to commercially available dyes and pigments, there are also publicly known dyes and pigments described in various documents (for example, "Dye Handbook" edited by the Organic Synthesis Science Society, published in 1972, "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1978). 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, A system that utilizes the azo coupling reaction of diazosulfonates with naphthols, anilines, activated methylenes, etc.; reactions of hexamethylenetetramine with ferric ions and gallic acid, and phenolphthalein-
Chelate-forming reactions such as the reaction of complexonic acid with alkaline earth metal ions; stearic acid secondary
Redox reactions such as the reaction between iron and pyrogallol and the same 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. Examples include those described in Japanese Patent Application Laid-Open No. 55-27253. Among these, (1) triarylmethane-based coloring agents and (3) xanthene-based coloring agents are preferred because they tend to 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-cyclohexylmethylamino-
Examples include 6-methyl-7-anilinofluorane and 3-diethylamino-7-o-chloroanilinofluorane, which may be used alone or in combination. As a color developer, a phenolic compound, an organic acid or its metal salt, an oxybenzoic acid ester,
Acidic 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. Further, an oil-absorbing white pigment can also be used in combination to diffuse and fix the capsule contents. 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 waxes such as higher fatty acid amides such as stearic acid amide, nilucic acid amide, palmitic acid amide, ethylene bisstearamide or higher fatty acid esters, phenyl benzoate derivatives, and aromatic ether derivatives. , or urea derivatives, but are not limited thereto. Other color forming agents/color developing agents include, for example, phenolphthalein, fluorescein, 2′,
4',5',7'-tetrabromo 3,4,5,6-tetrachlorofluorescein, telibromophenol blue, 4,5,6,7-tetrabromophenolphthalein, eosin, aurin cresol red, Examples include 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 morpholines, piperidines, amidines, formazines, and pyridines. Specific examples of these include, for example, ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-bezylimidazole, and 4-fluorene. enylimidazole, 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,
These include 2-amino-benzothiazole and 2-benzoylhydrazino-benzothiazole. The color image forming material of the present invention is a polymerizable compound of 100%
It is used in a proportion of 0.5 to 20 parts by weight, particularly preferably 2 to 7 parts by weight. 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. The microcapsules used in the present invention can be produced by methods known in the art. For example, US patent
2800457 and 2800458, a method using coma cellvation of a hydrophilic wall-forming material, U.S. Patent No. 3287154, British Patent No. 990443, Japanese Patent Publication No. 38-19574, Japanese Patent Publication No. 42-446, Showa 42-771
Interfacial polymerization method, US patent as seen in No.
3,418,250 and 3,660,304; methods using isocyanate-polyol wall materials as in U.S. Pat. No. 3,796,669;
Methods using isocyanate wall materials as found in U.S. Pat. No. 3,914,511; U.S. Pat. No. 4,001,140;
A method using a urea-formaldehyde-based or urea-formaldehyde-resorcinol-based wall forming material as seen in US Pat. No. 4,087,376 and US Pat. , the in situ method by polymerization of monomers as seen in Japanese Patent Publication No. 36-9163 and Japanese Patent Publication No. 51-9079, British Patent No. 952807,
Electrolytic dispersion cooling method as seen in No. 965074, U.S. patent
3111407, and the spray wing method as seen in British Patent No. 930422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall. The microcapsule wall of the present invention is particularly effective when using a microencapsulation method by polymerizing a reactant from inside an oil droplet. That is, it has a uniform particle size within a short time,
Capsules suitable as recording materials with excellent shelf life can be obtained. For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and a second substance that reacts with it to form the capsule wall (e.g., polyol, polyamine) are mixed into the oily liquid to be encapsulated, emulsified and dispersed in water, and then By increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall. At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid. In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat.
No. 3793268, Special Publication No. 48-40347, No. 49-24159,
It is disclosed in JP-A-48-80191 and JP-A-48-84086, and they can also be used. Examples of polyvalent isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4' -diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenylmethane-4,
4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,
2-diisocyanate, cyclohexylene-1,
2-diisocyanate, cyclohexylene-1,
Diisocyanates such as 4-diisocyanate,
Triisocyanates such as 4,4',4''-triphenylmethane triisocyanate, toluene-2,4,6-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetra Isocyanates such as tetraisocyanates, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and hexanetriol. There are isocyanate prepolymers such as adducts. Polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers. Ethylene glycol, which also uses the following polyols:
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptandinol, 1,
8-octanediol, propylene glycol,
2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 2,
2-dimethyl-1,3-propanediol, 2,
4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol,
1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol,
1,2,6-trihydroxyhexane, 2-phenylpropylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1, 4-di(2-hydroxyethoxy)benzene, condensation products of aromatic polyhydric alcohols such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, m-xylylene glycol, α,α′-dihydroxy- p-diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p,p'-dihydroxydiphenylmethyl)benzyl alcohol, adduct of ethylene oxide to bisphenol A, bisphenol A
Examples include adducts of propylene oxide. The polyol is preferably used in a proportion of hydroxyl groups of 0.02 to 2 moles per mole of isocyanate groups. Polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine,
p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5
Examples include -dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric materials. When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble anionic polymers, nonionic polymers, and amphoteric polymers. As the anionic polymer, both natural and synthetic polymers can be used, and examples thereof include those having -COO ^- , -SO ^- ₃ groups, and the like. Specific anionic natural polymers include gum arabic and alginic acid.
Carboxymethyl cellulose is a semi-synthetic product,
Examples include phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfonic acid. Synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol. Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose. Examples of amphoteric compounds include gelatin. These water-soluble polymers are used as a 0.01 to 10 wt% aqueous solution. The particle size of microcapsules is
Adjusted to 20μ or less. At least a polymerizable compound and a color image-forming substance are encapsulated in such microcapsules. In this case, silver halide, a reducing agent, etc. are usually also encapsulated in the capsule, but in that case, the silver halide and reducing agent are first dispersed or dissolved in a polymerizable compound in which a color image-forming substance is dissolved. This is used as an oil phase, and this is mixed with an aqueous phase in which a hydrophilic polymer compound is dissolved to emulsify and disperse to form an emulsion. Simultaneously or subsequently with this emulsifying dispersion, a wall can be formed at the oil/water interface of the emulsion particles by a well-known method. The method for making microcapsules is not limited to this, and various methods can be applied. The size of the capsule used in the present invention is 80 μm or less, and preferably 20 μm or less from the viewpoint of storage stability and ease of handling. Also, if the capsules are too small, they may disappear into the pores or fibers of the matrix.
Although this cannot be said unconditionally because it depends on the properties of the substrate or support, it is preferably 0.1μ or more. The capsule used in the present invention does not substantially change under pressure of about 10 kg/cm ² or less, and it is preferable that it breaks when a pressure higher than this is applied, but the magnitude of the pressure at which this breakage occurs depends on the application. Although it is not limited to a specific value as it can be changed by the pressure, it is preferable to destroy it at a pressure of about 500 kg/cm ² or less. These pressure characteristics can be controlled by the particle size of the capsule, the thickness of the capsule wall, and the type of wall material used. In order to change the thermal reactivity of the photosensitive material of the present invention, hydroxy compounds, carbamate ester compounds, aromatic methoxy compounds, and organic sulfonamide compounds described in Japanese Patent Application No. 60-25838 are added to microcapsules or microcapsules. Can be used outside. These compounds appear to alter the glass transition temperature of the microcapsule wall. Various image formation accelerators can be used in the present invention. The image forming accelerator has functions such as promoting the redox reaction between the silver salt oxidizing agent and the reducing agent, and promoting the transfer of the image forming substance from the photosensitive material layer to the image receiving layer. They are also classified as base precursors, oils, thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound may have multiple functions. many. Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates; ammonium hydroxide as inorganic bases; hydroxides of quaternary alkylammonium; hydroxides of other metals, etc.; 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 are decarboxylated by heating, compounds that release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothsen rearrangement, and Beckman rearrangement. Compounds that emit bases and compounds that generate bases by electrolysis or the like are preferably used. A preferred base precursor of the former type that generates a base upon heating is described in British Patent No.
Salts of trichloroacetic acid described in No. 998949 etc., salts of α-sulfonylacetic acid described in U.S. Patent No. 4060420,
Salts of propiolic acids described in JP-A No. 59-180537, 2-carboxycarboxamide derivatives described in U.S. Pat. No. 4,088,496, thermally decomposable products using an alkali metal or alkaline earth metal in addition to an organic base as the base component salts with acids (JP-A-59-195237), hydroxamic carbamates described in JP-A-59-168440 that utilize lotusene rearrangement, and aldos described in JP-A-58-31614 that produce nitriles by heating. Examples include xime carbamates. others,
Base precursors described in British Patent No. 998945, US Patent No. 3,220,846, Japanese Patent Application Laid-Open No. 50-22625, British Patent No. 2,079,480, etc. are also useful. The following compounds can be mentioned as compounds that generate bases by electrolysis. For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation. Through this reaction, carbonates of alkali metals and organic bases such as guandines and amidines can be obtained extremely efficiently. In addition, methods using electrolytic reduction include the production of amines by the reduction of nitro and nitroso compounds; the production of amines by the reduction of nitriles; the production of p-aminophenols and p-aminophenols by the reduction of nitro compounds, azo compounds, azoxy compounds, etc. - Generation of phenylene diamines and hydrazines, etc. In addition to being used as bases, p-aminophenols, p-phenylenediamines, and hydrazines can also be used directly as color image-forming materials. Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of various inorganic salts. As the oil, a high boiling point organic solvent used as a solvent during emulsification and dispersion of hydrophobic compounds can be used. Thermal solvents are solid at normal temperatures, and function as solvents by melting near the development temperature, such as ureas, urethanes, amides, pyrudines, sulfonamides, sulfones, sulfoxides, esters, and ketones. Compounds of ethers and ethers that are solid at temperatures below 40°C can be used. Examples of the surfactant include pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231. Compounds that interact with silver or silver ions include imides, nitrogen-containing heterocycles described in JP-A-59-177550, thiols, thioureas, and thioethers described in JP-A-59-111636. be able to. The image formation accelerator may be incorporated into either the photosensitive material or the image-receiving material, or may be incorporated into both.
The layer to be incorporated may also be incorporated in the emulsion layer, intermediate layer, protective layer, image-receiving layer, and any layer adjacent thereto. The same applies to a form in which a photosensitive layer and an image-receiving layer are provided on the same support. The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination. In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited. In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development. The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305, compounds that release acid by lotusene rearrangement described in Japanese Patent Application No. 59-85834, and the like. Examples of electrophilic compounds that undergo a substitution reaction with a base when heated include the compounds described in Japanese Patent Application No. 85836/1983. The image-receiving element of the present invention is an element for fixing a color image-forming substance emitted from the photosensitive element, and is coated on the same support as the photosensitive element, or is coated on the same support as the photosensitive element, or is separate from the photosensitive material containing the photosensitive element. It is coated on a support to constitute an image-receiving material. Furthermore, the image receiving element of the present invention may have at least one layer containing a mordant, if necessary.
If the image-receiving element is located on the surface, it can be provided with a protective layer. Further, if necessary, it may be constructed of two or more layers using mordants having different mordant powers. When a mordant is used in the image-receiving layer, any mordant can be selected from among the mordants used in diffusion transfer type light-sensitive materials, and among them, polymer mordants are particularly preferred. What is a polymer mordant here?
These include polymers containing a tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cation groups. Polymers containing vinyl monomer units having a tertiary amino group are described in Japanese Patent Application No. 169012/1982, Patent Application No. 166135/1982, etc., and polymers containing vinyl monomer units having a tertiary imidazole group are described in Specific examples include Japanese Patent Application No. 58-226497;
58-232071, U.S. Pat. No. 4,282,305;
It is described in No. 4115124, No. 3148061, etc. Preferred specific examples of polymers containing vinyl monomer units having quaternary imidazolium salts include British Patent Nos. 2056101, 2093041, and British Patent Nos.
1594961, U.S. Patent No. 4124386, U.S. Patent No. 4115124
No. 4273853, No. 4450224, Japanese Unexamined Patent Publication No. 1973-
It is described in No. 28225 etc. Other preferred specific examples of polymers containing vinyl monomer units having quaternary ammonium salts include U.S. Pat.
No. 3958995, Patent Application No. 58-166135, No. 58-169012
No. 58-232070, No. 58-232072 and No. 59
-Described in No. 91620, etc. In the present invention, a solvent can be used in conjunction with the encapsulation of the polymerizable compound and color image forming substance. A solvent can also be used when introducing a reducing agent, color developer, etc. into necessary elements. For example, a solution in water or a hydrophilic organic solvent can be coated directly onto the support, optionally with a binder, or can be introduced into the necessary elements by known methods, such as the method described in U.S. Pat. No. 2,322,027. can do. By using a solvent in the microcapsules, it is also possible to control the degree of destruction of the capsules upon pressurization and the amount of transfer of the color image-forming substance within the capsules to the image receiving element.
The amount of solvent used in the capsule depends on the polymerizable compound.
A ratio of 1 to 500 parts by weight per 100 parts by weight is preferred. Natural oils or synthetic oils can be used alone or in combination as the solvent used in the present invention.
Examples of these solvents include cottonseed oil, kerosene,
Aliphatic ketones, aliphatic esters, paraffins, naphthenic oils, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, and 1-phenyl-1-xylylethane, 1-phenyl-1-p-ethyl phenylethane , 1,1'-ditolylethane and the like. Phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), Benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (e.g. tributyl trimesate), ethyl acetate,
Examples include lower alkyl acetates such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone. The binders used in the photosensitive material and image-receiving material of the present invention may be contained alone or in combination. This binder can be mainly hydrophilic. Hydrophilic binders are typically transparent or translucent, such as gelatin, gelatin derivatives,
Proteins such as cellulose derivatives, starch,
These include natural substances such as polysaccharides such as gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes. 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,
Not only paper, wood-free paper, synthetic paper, metals and their analogues are used, but also acetyl cellulose film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and films or resin materials related thereto. is included. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Patent No. 3634089,
The polyester film described in No. 3725070 is preferably 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 irradiation dyes, pigments (including white pigments such as titanium oxide), water-releasing agents, and thermal It may contain a polymerization inhibitor, a surfactant, a heat solvent, a dispersed vinyl compound, and the like. Various exposure means can be used in the present invention. The latent image is obtained by imagewise 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 types of LEDs that emit green light, red light, and infrared light are used, and the emulsion parts that are sensitive to these lights are
It may be designed to include 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
This information is read by a light-receiving element such as a CCD, and is stored in the memory of a computer, etc., and then subjected to so-called image processing to be modified as necessary. This image information is then reproduced on a CRT and used as an image-like light source. Alternatively, there is a method in which three types of LEDs are directly emitted 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, the photosensitive material may be heated in a bath containing a liquid inert to the photosensitive material, such as a fluorine-based liquid. 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 dielectric 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 1 second 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. "Examples" The photosensitive recording material of the present invention will be specifically described below using Examples. Example 1 Method for manufacturing image-receiving material 65 parts of light calcium carbonate, 35 parts of aluminum hydroxide (Showa Denko H-10), 1.8 parts of styrene-α-methylstyrene decamer and zinc 3.5-di-α-methylbenzylsalicylate. Kneaded and ground product with 8.2 parts,
10 parts of zinc oxide and 1 part of sodium hexametaphosphate were dispersed in 200 ml of water, and then treated with a sand mill to obtain a dispersion having an average particle size of 2.6 μm. To this were added 9 parts of polyvinyl alcohol, 20 parts of carboxy-modified SBR latex (48%), and 110 parts of water, and the mixture was stirred well. This is added to a base paper weighing 43g/ ^m2 as a solid content.
It was coated at a density of 5.2 g/m ² and dried at 90°C. Manufacturing method of photosensitive material 15 g of silver behenate was suspended in 200 ml of methanol in a dark room, and a solution of 20 mg of ammonium bromide and 5 mg of ammonium iodide dissolved in 10 ml of methanol was added little by little. After stirring vigorously for 10 minutes, the precipitate was collected by filtration to obtain a photosensitive silver behenate emulsion. 2g of the above silver behenate emulsion, 5g of N,N'-diacryloylpiperazine, 3g of pentaerythritol tetraacrylate, 0.5g of crystal violet lactone, 6g of phenylxylylethane, tolylene diisocyanate and trimethylolpropane (3:1) 1 g of the adduct, 0.3 g of an ethylenediamine propylene oxide (1:4) adduct, and 4 ml of ethyl acetate were mixed and dissolved. The above solution was mixed with a solution of 3 g of polyvinyl alcohol in 30 ml of water, and dispersed using a sand mill. Next, add 100ml of water while stirring, and heat at 50℃ for 2 hours.
Capsules were obtained by heating for hours. Average particle size is 10μm
It was hot. 5% SBR was added to this capsule dispersion liquid to make a coating liquid, and this was applied onto a polyethylene terephthalate film to a wet film thickness of 40 μm.
Dry. Next, on top of this, a solution of 250 mg of m-dimethylaminophenol dissolved in 5 ml of methanol, and 1% aqueous solution of sodium dodecylbenzenesulfonate were added.
ml, a mixture of 5 mg of formaldehyde sodium bisulfite adduct and 30 ml of a 4% aqueous gelatin solution was coated and dried to obtain a light-sensitive material. The obtained photosensitive material is exposed to a tungsten light bulb.
After imagewise exposure at 2000 lux for 5 seconds, it was heated for 30 seconds on a hot plate heated to 90°C. Then, when the photosensitive material and the image-receiving material were stacked together and passed through a pressure roller, a clear blue image corresponding to the unexposed areas was obtained. Example 2 [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 to 50ml.
And so. (Solution C) 2.38 g of potassium bromide and 0.17 g of potassium iodide were dissolved in water 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 continuing stirring for 5 minutes after this addition,
This liquid was filtered, 200 ml of a 20% isopropyl alcohol solution of polyvinyl butyral was added to this liquid, and the mixture was dispersed in a homogenizer for 20 minutes to form an emulsion. The yield of this emulsion was 250g. (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) 11.9 g of potassium bromide and 0.83 g of potassium iodide were dissolved in water 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, this liquid was filtered, and then 200 ml of a 20% inpropyl alcohol solution of polyvinyl butyral was added thereto, and the mixture was dispersed using a homogenizer for 20 minutes to form an emulsion. The yield of this emulsion was 250g. (Emulsion) The following solution was prepared. (Solution A) 12g gelatin, 5.6g sodium chloride
and 0.6 g of potassium bromide were dissolved in 1000 ml of water. (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 a period of 90 minutes. After removing excess salt from the produced silver chlorobromide emulsion by 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 with a yield of 400 g. Obtained. (Emulsion) The following solution was prepared. (Solution A) 10 g of gelatin and 3 g of sodium chloride were dissolved in 1000 ml of water. (Solution B) 100 g of silver nitrate was dissolved in water to make 600 ml. (Solution 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
After washing and desalting a 0.35μ monodisperse cubic silver chlorobromide emulsion,
An emulsion was obtained which was chemically sensitized with sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. The yield of emulsion is
It was 600g. (Solvent) 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.
Meanwhile, 6 g of methylene chloride, component (a) shown in Table 1
0.7g and (b) 2.1g, and the coloring agent 3-
2.1 g of diethylamino-6-chloro-7-anilinofluorane was dissolved and added to the above solution to form an oil phase. Separately for comparison, component (c) was removed, component (a), (b), and (c) were replaced with 3.5 g of benzoin butyl ether and dissolved in the monomer mixture, and component (a), In place of (b) and (c), emulsions () to () and component d first
A mixture was prepared in the proportions shown in the table. Meanwhile, a mixture of 17.5 g of 10% gum arabic aqueous solution, 18.8 g of 12% isobutylene/anhydrous maleic () aqueous solution, and 26.8 g of distilled water was adjusted to pH 3.5 with sulfuric acid, and further 4.6 g of urea and 0.6 g of resorcin were added. The above monomer mixture was emulsified and dispersed in the solution to give a thickness of 3μ.
Next, add 12.9 g of 36% formalin and mix to 60 ml.
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 5g 15% polyvinyl alcohol aqueous solution, 3.47 g of distilled water,
0.57g of starch was added to prepare a coating solution. Apply this to art paper using coating rod 10,
The photosensitive sheets 1 to 5 were obtained by drying at 50° C. for 15 minutes. Meanwhile 0.6g of 48% SBR latex in 21.8g of water,
10% etherified starch aqueous solution 4g, zinc carbonate
2.1 g, 1.3 g of 50% aqueous sodium silicate solution, 0.1 g of sodium hexametaphosphate, and 13 g of acid clay were added, and 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. These exposed photosensitive sheets and image receiving sheets 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) was significantly increased compared to the cases in which no silver halide emulsion was used (Comparative Examples 1 and 2). can be seen. Example 3 Using silver halide emulsion () or () or () instead of components (a), (b), and (c) in the microcapsule preparation example in Example 2,
and color former 3-diethylamino-6-chloro-7
- Three capsule solutions (α), (β), (γ) were prepared in exactly the same manner as in Example 1, except that each of the substances shown in Table 2 was used in place of 2.1 g of anilinofluorane.
Prepare.

[Table] 5 g of each solution of the capsules thus obtained was 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 the mixture to prepare a coating solution.
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] Further, 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 pressed in the same manner, a positive image can be obtained on the image receiving sheet. .

Claims (1)

[Claims] 1 At least photosensitive silver halide on the support,
It has a reducing agent, a polymerizable compound, and a color image-forming substance, and is characterized in that at least the photosensitive silver halide, the polymerizable compound, and the color image-forming substance are encapsulated in the same microcapsule. photosensitive material.