JPH0349094B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a heat-developable color photographic material, and more particularly to a heat-developable color photographic material having excellent image density and storage stability over time. [Prior Art] The conventionally known color photography method using photosensitive silver halide is superior to other color photography methods in terms of photosensitivity, gradation, image quality, etc., and is the most widely put into practical use. It's here. however,
In this method, wet processing is used for steps such as development, bleaching, fixing, and washing, which is time-consuming and labor-intensive, and there are concerns that processing chemicals may cause pollution to the human body, or There are many problems, such as concerns about contamination of people by treatment chemicals, and furthermore, the labor and cost of waste liquid treatment. Therefore, there has been a demand for the development of a method for forming color images that allows dry processing. In recent years, with the development of computers, word processors, and various medical diagnostic devices, CRTs have become more color-based, and the demand for high-quality color hard copies is rapidly increasing. Among them, thermal transfer printers are the mainstream and have even been commercialized. However, there is a strong desire to shorten printing time, and there is a desire to develop a method for increasing thermal transfer efficiency. For example, methods for obtaining color hard copies of higher image quality by dry processing using silver halides and organic silver salts are disclosed in JP-A-57-179840 and JP-A-57-186744.
No. 57-198458 and Japanese Patent Application No. 57-122596. However, even in the techniques disclosed above, the thermal transfer density of the thermally transferable dye released in an imagewise manner to the image-receiving layer is not necessarily sufficient, and there is still a desire to develop a method for increasing the thermal transfer density. However, in the above techniques, dye release aids are generally added to the photosensitive layer to increase the thermal transfer density. However, while dye release aids increase the amount of dye released, they have an adverse effect when present in the photosensitive layer, resulting in deterioration of the performance of the photosensitive layer during storage over time, and as a result, the transferability of the thermally transferable dye to the image-receiving element. It also has the drawback that the thermal transfer density decreases significantly and fog increases along with it. Generally, the dye release aid specifically includes a base, a base release agent, or a water release compound;
It decomposes during heat development and releases base and water to activate the formation and release of heat transferable dyes. These dye release aids decompose to varying degrees during storage over time, adversely affecting the organic silver salts and dye-donating substances in the photosensitive layer, and greatly deteriorating the performance of the photosensitive layer. However, no attempt has been made in the prior art to improve this serious drawback. Among the photographic constituent layers of a light-sensitive element, the light-sensitive layer containing an organic silver salt and a dye-providing substance is different from the light-sensitive layer containing an organic silver salt and a dye-providing substance, even if a dye-releasing agent is added to another layer, such as a protective layer or an intermediate layer, during the manufacturing process or during storage over time. Since the dye release aid easily diffuses and moves, the above method does not provide a fundamental solution to prevent the adverse effects of the dye release aid. [Object of the Invention] Therefore, an object of the present invention is to provide a heat-developable color photographic material having excellent storage stability over time. Another object of the present invention is to provide a heat-developable color photographic material in which fog and staining are reduced and sufficient maximum density is obtained. [Structure of the Invention] The above object of the present inventors is to provide a heat-developable photosensitive element having a photographic constituent layer containing an organic silver salt and a heat-transferable dye-providing substance, and a heat-developable photosensitive element having a photographic constituent layer containing an organic silver salt and a heat-transferable dye-providing substance; a heat-developable color photographic material having an image-receiving element having an image-receiving layer capable of receiving a thermally transferable dye to be provided, characterized in that the image-receiving element contains a dye-releasing aid which is a base or a base-releasing agent. shall be. The heat-transferable dye-providing substance capable of providing the heat-transferable dye of the present invention is thermally non-diffusible and substantially does not cause intralayer or interlayer diffusion even when heated. The heat-developable color photographic material of the present invention simultaneously provides a silver image having a negative-positive relationship with the original and a heat-transferable dye in the areas corresponding to the silver image by simply performing heat development after image exposure. I can do it. That is, when the heat-developable color photographic material of the present invention is imagewise exposed and thermally developed, an oxidation-reduction reaction occurs between the organic silver salt oxidizing agent and the reducing agent, producing a silver image in the exposed areas. In this step, the reducing agent is oxidized to an oxidant by an organic silver salt oxidizing agent. This oxidant reacts with a dye-providing substance that can provide a heat-transferable dye contained in the photographic material and provides the heat-transferable dye to the image-receiving element. There are two formats. The present invention can use either format. One type is when the oxidant and the dye-donating substance cause a coupling reaction, resulting in the provision of a heat transferable dye; another type is when the oxidant and the dye-donating substance cause a cross-oxidation reaction. , so that the oxidized dye-donor material cleaves in the presence of the dye release aid to provide a thermally transferable dye. Further, the coupling reaction format is further classified into two methods. That is, there are cases in which a dye formed by coupling the oxidant and a dye-donating substance are used as a heat-transferable dye, and a case in which the formed dye is not used but a leaving group that leaves the coupling site by a coupling reaction is used as a heat-transferable dye. This is when you use it. The above can be summarized as follows.

[Thermal transferable dye-providing substance]

The dye-donating substance used in the present invention includes a sulfo group or a salt thereof, a carboxy group or a salt thereof,
It is a compound that has a water-soluble group such as a sulfonamide group or a salt thereof in its molecule and releases or forms a diffusion transferable dye upon thermal development.Diffusion transferable dyes usually include a sulfo group, a carboxyl group, A hydrophobic dye that does not have a polar group such as a sulfonamide group is used. Therefore, as the dye-providing substance used in the present invention, compounds represented by the following general formula (1) to which these hydrophobic dyes are provided by thermal development can be used. General formula (1) A-B-C (coupling-release dye utilization format) [In the formula, A represents a coupler residue, and B represents a simple bond or a divalent bonding group. C represents a hydrophobic dye or dye precursor residue.
Here, the coupler residue of A has a hydrophilic group such as a sulfo group or a salt thereof, a carboxyl group or a salt thereof, or a sulfonamide group. ] Particularly preferred dye-providing substances in the present invention are:
A in the general formula (1) is active methylene, active methine,
Preferred substrates are phenol and naphthol residues and are represented by the following general formulas (2) to (8).

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【formula】

[Formula] In the formula, R ¹ , R ² , R ³ , RP, R ⁵ , R ⁶ , R ⁷ and R ⁸
are a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), a sulfo group, a carboxyl group, a sulfonamide group, an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms), such as methyl, Represents ethyl, butyl, t-octyl, t-dodecyl group, n-pentadodecyl group, cyclohexyl group, etc. Also represents an alkyl group substituted with an aryl group (benzyl group, phenethyl group, etc.), substituted/unsubstituted aryl groups (e.g. phenyl, naphthyl, tolyl, mesityl),
Acyl groups (e.g. acetyl group, tetradecanoyl group, pivaloyl group, substituted/unsubstituted benzoyl group, etc.), alkyloxycarbonyl groups (e.g. methoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenolic cycarbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, etc.), arylsulfonyl group (e.g. phenylsulfonyl group, etc.), carbamoyl group (e.g. substituted or unsubstituted Substituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, substituted/unsubstituted phenylcarbamoyl group (e.g., 2-dodecyloxyphenylcarbamoyl group, etc.), substituted/unsubstituted acylamino groups (e.g., n-butylamide group, laurylamide group, optionally substituted β-phenoxyethylamide group, phenoxyacetamide group) , substituted/unsubstituted benzamide groups such as benzamide, β-methanesulfonamidoethylamide groups,
β-methoxyethylamide group, etc.), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, octadecyloxy group, etc.), sulfamoyl group (e.g. methylsulfamoyl group, n -dodecylsulfamoyl group, substituted/unsubstituted phenylsulfamoyl group, etc.), sulfonylamino group (e.g. methylsulfonylamino, tolylsulfonylamino)
Or represents a hydroxy group. However, at least one of R ¹ , R ² , R ³ and R ⁴ and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ are ballast groups that reduce thermal diffusivity, such as sulfo groups. , a group containing a hydrophilic group such as a carboxy group or a sulfonamide group. Furthermore, at least one set of R ¹ and R ² , R ³ and R ⁴ , and at least one set of R ⁵ and R ⁶ , and R ⁶ and R ⁷ are bonded to each other, and saturated or unsaturated 5- 6
It may form a membered ring. In addition, R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom,
Halogen atom (preferably chlorine atom, bromine atom,
iodine atom), alkyl groups (preferably alkyl groups having 1 to 24 carbon atoms, such as methyl, ethyl, substituted or unsubstituted alkylamide groups, such as laurylamide groups, optionally substituted phenoxyalkylamide groups, such as alkyl substituted phenoxyacetamide group, substituted/unsubstituted arylamide group, etc.)
represents. R ¹² is an alkyl group (preferably one carbon atom
~24 alkyl groups (e.g. methyl, butyl, heptadecyl, etc.), alkoxy groups (preferably represent alkoxy groups having 1 to 18 carbon atoms, e.g. methoxy, ethoxy, octadecyloxy), arylamino groups (e.g. anilino groups, and further halogens) , represents an anilino group substituted with a substituent such as alkyl, amide or imide), and substituted
Unsubstituted alkylamides (e.g. laurylamide, optionally substituted phenoxyacetamide, phenoxybutanamide, etc.), substituted and
unsubstituted arylamides (e.g. benzamide,
represents a benzamide group substituted with a halogen or an alkyl, alkoxy, or amide group. Further, R ¹³ represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) or a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group, etc.). Furthermore, R ¹⁴ represents an arylamino group (for example, an anilino group or an anilino group further substituted with a halogen, alkyl, phenoxy, alkylamido, arylamido, imido group, etc.). In the general formula (1), B represents a simple bond, ie, a case where a coupler residue and a diffusible dye residue or a diffusible dye precursor residue are directly bonded, and a case where B is a divalent bonding group. Examples of divalent bonding groups include -O-, S, -NH-CO-,

[Formula]-N=N-,

【formula】

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【formula】

[Formula] etc. In the general formula (1), the diffusible dye residue represented by C is preferably a monoazo dye residue, an anthraquinone dye residue, a nitrodiphenylamine dye residue, or the like. Another useful type of dye-donating substance is a dye-forming compound represented by general formula (9) below. General formula (9) A'-B' (coupling-forming dye usage format) where A' is a hydrophobic coupler residue,
This does not include water-soluble groups such as sulfo groups, carboxyl groups, and sulfonamide groups. B' is a group that can be separated from the coupler by a coupling reaction, and represents a sulfo group, a carboxyl group, a sulfonamide group, or a group having these groups. Particularly preferred compounds here include couplers that can react with oxidized color developing agents to form sublimable or volatile dyes, as described in Japanese Patent Application No. 57-229650 by the present inventors. These couplers produce hydrophobic, heat-transferable dyes through a coupling reaction with the oxidized product of a color developing agent formed by heat development, and are represented by the following general formulas (10) to (15). Compounds represented by are preferred.

【formula】

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【formula】

【formula】 [Other dye-donating substances]

The dye-donating substance used in the present invention can be synthesized in accordance with the methods described in, for example, Japanese Patent Application Laid-open No. 186744/1982 and Japanese Patent Application No. 229671/1983. Yet another type of dye-providing substance that can be used in the present invention is represented by the following general formula (16). General formula (16) A″−SO ₂ −B″ (cross oxidation format) Here, A″ represents a reducing substrate that can be cross-oxidized by the oxidant produced when the reducing agent is oxidized with an organic silver salt, and B″ represents a heat-transferable dye-forming portion. Preferred reducing substrates are, for example, disclosed in JP-A-57-
Publication No. 198458 (hereinafter referred to as Cross Oxidation Publication)
The general formula (), (), (), (), (), (
)
and (). Further, as for preferable specific examples of the reducing substrate A'', for example, see pages 6 to 7 of the above-mentioned Cross Oxidation Publication.
You can list the ones listed on the page, and also,
Examples of dyes that can be used as image-forming dyes are listed in the lower right column of page 7 of the publication, and further specific examples for each hue of yellow, magenta, and cyan are listed in the lower right column of page 7 of the publication. Examples of preferable image-forming dyes include yellow, magenta, and cyan, which are listed on pages 11 to 14 of the publication. Further, as specific examples of the dye-providing substance, the substances described in the upper right column on page 12 to page 14 of the publication can be mentioned.
These dye-donating substances can be synthesized by the synthesis methods described in the above-mentioned Cross Oxidation Publication and Japanese Patent Application Laid-Open No. 179840/1983. [Binder for Photosensitive Layer] The above-mentioned thermally non-diffusible dye-providing substance according to the present invention is used by being contained in the heat-developable photosensitive layer or other photographic constituent layers. Any hydrophobic polymer may be used, and these may be used alone or in combination. Among the above binders, hydrophilic binders include transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch, or natural substances such as polysaccharides such as gum arabic, and polyvinylpyrrolidone. , synthetic polymers such as water-soluble polyvinyl compounds such as acrylamide polymers, and the like. For example, the transparent synthetic polymer used as a hydrophilic binder in the present invention is disclosed in US Pat.
It is described in No. 3142586, No. 3193386, No. 3062674, No. 3220844, No. 3287289, No. 3411911, etc. Useful polymers include alkyl acrylates, alkyl methacrylates,
Examples include water-insoluble polymers containing acrylic acid, sulfoalkyl acrylate, or sulfoalkyl methacrylate as monomers, and those having circulating sulfobetaine units as described in Canadian Patent No. 774054. Preferred polymers include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene styrene copolymer, vinyl chloride. Examples include vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate phthalate, and the like. Among these polymers, especially polyvinyl butyral, polyvinyl acetate ethyl cellulose,
Preferred are polymethyl methacrylate, cellulose acetate butyrate, and the like. If necessary, two or more types may be used in combination. The amount of the hydrophobic polymer binder is 1/10 to 10 times, preferably 1/4 to 4 times, the weight of the organic silver salt oxidizing agent described below. In the present invention, it is most advantageous for the photosensitive function and the developable function to utilize a heat-developable photosensitive element using an organic silver salt. This is because in terms of photosensitivity, it is possible to improve sensitivity or spectral sensitization by using silver halide brought into catalytic contact with an organic silver salt. Furthermore, it is possible and, in fact, effective to improve the image quality by adding halation or anti-irradiation dyes in the method of the present invention in which a color image is diffusely transferred and separated from a silver image. In terms of developability, it has the advantage that it is easy to relate the dissolution physical development reaction of the organic silver salt caused by heating to the provision of a thermally transferable dye from a dye-providing substance. That is, in the method of the present invention, by appropriately setting the dissolution physical development reaction of an organic silver salt, the reaction in which a thermally transferable dye is released or provided using the reaction, and the conditions for these thermal transfers, It is also possible to obtain clear color transfer images by heating (thermal development) only once. The photosensitive layer of the heat-developable photographic element used in the present invention basically contains (1) a binder, (2) an organic silver salt, (3) if necessary a photosensitive silver halide, (4) )
Contains a thermally non-diffusible dye donor and (5) a reducing agent.
However, these are not necessarily contained only in the photosensitive layer, but may also be contained, for example, in a layer adjacent thereto. Optionally, a reducing agent may be included in the image-receiving layer. [Organic silver salt] As the organic silver salt used in the present invention,
Organic acid silver salts such as gallotsucate silver salt, oxalate silver salt, especially fatty acid silver salts such as behenate silver salt, stearate silver salt, palmitate silver salt, imidazole silver salt, benzotriazole silver salt, Nitrogen acid silver salts such as 4-sulfobenzotriazole silver salt, 5-nitrobenzotriazole silver salt, and 4-hydroxybenzotriazole silver salt, as well as thione silver salt, saccharin silver salt, 5-chlorsalicylaldoxime silver salt, etc. be. [Photosensitive silver halide] In addition, the photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver iodobromide. Examples include silver chemical. The above-mentioned photosensitive silver halide can be prepared by any method known in the photographic field, such as a single-jet method or a double-jet method. Silver halide gelatin emulsions prepared according to the procedure give favorable results. The photosensitive silver halide described above may also be chemically sensitized by any method known in the photographic field. Examples of such sensitization methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. This photosensitive silver halide may have coarse or fine grains, but the preferred grain size is about 1.5μ to about 0.001μ, more preferably about 0.5μ to about 0.05μ. be. Furthermore, as another method for preparing photosensitive silver halide,
It is also possible to cause a photosensitive silver salt-forming component to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming component is a halogen-releasing agent, and this method is well known in the field of heat-developable photographic materials. Additives include oxidizing agents, activators, stabilizers,
These include color toning agents, sensitizers, thermal antifoggants, printout inhibitors, spectral sensitizers, filter dyes, and the like.
These are described in detail in Research Disclosure No. 17029 (1978), and these can also be used in the present invention. According to the present invention, when the photosensitive layer of the photosensitive element and the image-receiving layer of the image-receiving element, which are in a stacked relationship with each other, are heated (thermally developed) after image exposure, the inventive agent (dye-releasing aid) is applied from the image-receiving element to the photosensitive layer. ) is released, thus promoting thermal development, and a sufficient concentration of heat transferable dye is released from the photosensitive layer to the image-receiving layer and dyed therein. At this time, the photosensitive layer may contain various thermal solvents and diffusion aids in order to increase the dyeing density of the thermally transferable dye in the image-receiving layer. [Dye release aid] The inventive agent (dye release aid) is an agent that enhances the formation and release of a dye by promoting the development, coupling reaction, and cross-oxidation reaction between an organic silver salt and a reducing agent. Base releasing agents or water releasing compounds are used. Among these dye release aids, bases or base release agents are particularly useful because they not only promote dye release but also the redox reaction between the organic silver salt oxidizing agent and the reducing agent. Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[ Examples include p-(dialkylamino)phenyl]methanes. U.S. Pat. No. 2,410,644 describes tetramethylammonium petaine iodide and diaminobutane dihydrochloride, and U.S. Pat. No. 3,506,444 describes organic compounds containing amino acids such as urea and 6-aminocaproic acid, which are useful. A base release agent releases a basic component upon heating. An example of a typical base release agent is British Patent No.
Described in No. 998949. Preferred base releasing agents are salts of carboxylic acids and organic bases; useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid; useful bases include guanidine, piperidine, morpholine, p-toluidine, 2-picoline, and the like. Guanidine trichloroacetic acid, described in US Pat. No. 3,220,846, is particularly useful. Aldonamides described in JP-A No. 50-22625 are preferably used because they decompose at high temperatures to produce bases. A water-releasing compound is a compound that decomposes during thermal development to release water and replaces a compound with a vapor pressure of 10 ^-5 Torr or more at a temperature of 100 to 200°C. These compounds are particularly known for transfer printing of fibers, and are known as NH ₄ Fe described in Japanese Patent Publication No. 88386/1986.
(SO ₄ ) _{2.12H 2} O etc. are useful. These dye release aids can be used in a wide variety of ways. 1/100 to 10 times molar ratio to silver,
In particular, it is preferably used in a range of 1/20 to 2 times. [Thermal solvent] The "thermal solvent" that can be used in the present invention is
It is a non-hydrolyzable organic material that is solid at ambient temperature but exhibits mixed melting points with other components at or below the heat treatment temperature used. Useful examples of the thermal solvent include compounds that can serve as solvents for developing agents, and compounds that are known to promote the physical development of silver salts using substances with a high dielectric constant. Useful thermal solvents include U.S. Pat.
Polyglycols described in No. 3347675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000;
Derivatives such as oleate esters of polyethylene oxide, beeswax, monostearin, -SO ₂
Compounds with a high dielectric constant having -, -CO- groups, such as acetamide, succinimide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, polar substances described in US Pat. No. 3,667,959, lactone of 4-hydroxybutanoic acid,
Methylsulfinylmethane, tetrahydrothiophene-1,1-dioxide, 1,10-decanediol, methyl anisate, biphenyl perate, etc. described in Research Disclosure Magazine, December 1976 issue, pages 26-28. Preferably used. The heat-developable color photographic material of the present invention may contain a diffusion aid. A diffusion aid is a non-hydrolyzable organic compound that is solid at ambient temperature but has a melting point below the heat treatment temperature used and is capable of penetrating into the image-receiving layer during heat treatment. . Preferred diffusion aids include diphenyl, o-phenylphenol, phenol, resorcinol, pyrogallol. A compound used as a heat solvent can be used as the diffusion aid. [Image-receiving element] The above-mentioned organic polymer materials used to create the image-receiving element (image-receiving layer) suitable for the purpose of the present invention are heat-resistant organic polymers with a glass transition temperature of 40°C or higher and 250°C or lower. It is made of molecular material and is used in the form of a film or resin plate. There are many points that are not clear regarding the mechanism by which the dye released or donated from the dye-donating substance enters the image-receiving element.
It is generally believed that at a processing temperature above the glass transition point, the thermal mobility of polymer chains becomes large, and as a result, dyes can enter the gaps between chain molecules. For this reason, by using an image-receiving element made of an organic polymer substance with a glass transition temperature of 40°C or higher and 250°C or lower, the dye-donor substance and the dye can be distinguished, and a clear image can be obtained in which only the dye is contained in the image-receiving element. Images can be formed. Examples of organic polymeric substances used in the image receiving element of the present invention include the following. To list them, polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives with substituents having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarsol, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyfluorinated ethylene trichloride, polyacrylonitrile, poly-N,N-dimethylallyl Polyacrylates with amide, p-cyanophenyl groups, pentachlorophenyl groups and 2,4-dichlorophenyl groups, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, Polytertiary butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate,
Examples include polyesters such as polyethylene terephthalate, polysulfones, bisphenol A polycarbonate, polycarbonates, polyanhydrides, polyamides, and cellulose acetates. Also, Polymer Handbook
2nbed (edited by J. Brandrup, EHImmergut) John
Also useful are synthetic polymers with glass transition temperatures above 40°C and below 250°C as described in Wiley & Sons publications. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful receiving surface elements include cellulose acetate films such as triacetate and diacetate, heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid,
Polyamide films made from combinations of hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, etc.; polyester films made from combinations of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol; polyethylene terephthalate films; Examples include polycarbonate film. These films may also be improved. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-
A polyethylene terephthalate film using 4-benzenesulfonic acid or the like as a modifier is effective. The image receiving layer of the image receiving element may be formed from a single layer or from multiple layers. Furthermore, the image-receiving layer has a portion or layer containing titanium white in or outside the image-receiving layer,
A white reflective layer may be formed. The image-receiving element of the present invention may also have an image-receiving layer formed by coating the above-mentioned organic polymer substance on a support such as glass, paper, or metal. In this case, the present invention agent may be contained in the image-receiving layer and/or the support. [Reducing agent] Further, reducing agents used in the present invention generally include phenols, sulfamide phenols, polyhydroxybenzenes, naphthols, hydroxybinaphthyls, methylene bisnaphthols, methylene bisphenols, ascorbic acids, 3 -pyrazolidones, pyrazolines,
There are pyrazolones, etc., but in the present invention,
A developer capable of oxidative coupling or diazo coupling with the dye-providing substance, such as aminophenols, paraphenylene diamines, sulfamide anilines, sulfamic acids, and hydrazones, is used alone or in combination with the developer. be able to. Depending on the purpose, the agent of the present invention may be dissolved in water or an organic solvent and then mixed with an organic polymer dispersion or an organic polymer solution to form a film or resin plate to prepare an image receiving element. is preferred. The amount of the present agent to be added is 0.05 to 10 times, preferably 0.1 to 2.0 times the amount of the organic polymer substance.
In the present invention, it is preferable not to add the present invention agent at all to the photosensitive layer or other photographic constituent layers of the photosensitive element, but depending on the purpose, for example, to accelerate initial development, it may be necessary to avoid adversely affecting the storage stability over time. It may be added to the photosensitive layer and other photographic constituent layers as long as it is in a very small amount. In addition, as an image receiving element containing the present invention agent, the thickness is 10 to
A 1000μ film may be used as it is, but it is also possible to prepare an aqueous dispersion of an organic polymer substance, or an aqueous solution or a solvent solution, add the present agent, and then add calcium carbonate as necessary. An image-receiving layer can be formed by adding a paint mixed with general pigments such as , titanium dioxide, and clay, and applying the mixture to a suitable support to a thickness of about 0.5 to 30 μm, which can be used as an image-receiving element. As for the support used for coating the image-receiving layer, a wide range of materials can be used as long as it can withstand the temperature during heat development treatment as described above, such as glass, paper, metal, and As well as analogs thereof, mention may be made of polyamide films, acetyl cellulose films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and films or resin materials related thereto. Further, the image-receiving element of the present invention may contain a reducing agent in addition to the present agent (dye release aid). This method is preferable since dye release aids and reducing agents are generally components that exhibit adverse effects in light-sensitive elements. In this case, the reducing agent is not substantially contained in the photosensitive element, but may be contained in a very small amount for a certain purpose, such as for initial development. [Specific Examples of Image-Receiving Elements] Typical specific examples of preparing an organic polymer layer (image-receiving layer) according to the present invention on a support as an image-receiving element will be described below. [Preparation Example 1] 200 ml of 10% aqueous dispersion of saturated polyester (Vylonal MD-1200 manufactured by Toyobo Co., Ltd.) on Paraita paper.
5 g of hydroxylamine sulfate as a dye release aid was added and dissolved in the solution, coated using a wire bar to a dry film thickness of about 6 μm, and dried to prepare an image receiving element. [Preparation Example 2] Add 25 ml of a slurry (solid content: 70%) of heavy calcium carbonate (Maruo Calcium Super 1500) to 100 ml of a 10% aqueous dispersion of saturated polyester containing the dye release aid used in Preparation Example 1. Preparation Example 1 by mixing
An image receiving element having an image receiving layer having a dry film thickness of about 9 μm was prepared in the same manner as described above. [Preparation Example 3] Saturated polyester pellets (Toyobo Byron)
200) After dissolving 20g in 150ml of methyl ethyl ketone, add 4-hydroxymethyl-4- as a reducing agent.
7 g of methyl-pyrazolidone and 3 g of triethylamine as a dye release aid were added and dissolved, and coated on a glass surface using a wire bar to prepare an image receiving element having an image receiving layer having a dry film thickness of about 5 μm. [Preparation Example 4] Saturated polyester aqueous dispersion 10 used in Preparation Example 1
% solution 100ml and polyvinylpyrrolidone 10% aqueous solution 50ml
Add 7 ml of guanidine trichloroacetic acid to the mixed solution.
After adding g and 10 g of titanium dioxide and stirring well, the mixture was coated on baryta paper to a dry film thickness of about 8 μm and dried to prepare an image-receiving element. The heat-developable photosensitive layer in the photosensitive element of the present invention is coated on the support of the photosensitive element or on the image-receiving element side, and its material is the same as that used for producing the above-mentioned image-receiving layer or image-receiving element. It may be the same organic polymer substance as . However, it is preferable to provide a barrier layer between the photosensitive layer and the support on the side of the photosensitive element in order to prevent thermal transfer of the heat-released or donated dye to the support, thereby reducing the transfer efficiency to the image-receiving element. and/or a barrier layer may be provided on the receiving element side. The barrier layer is preferably a hydrophilic colloid layer such as gelatin. [Exposure light source] In the present invention, imagewise exposure of the photosensitive element of the photographic material is performed by sunlight, a tungsten lamp, a fluorescent lamp, a mercury lamp, a halogen lamp, a xenon lamp, a laser beam, a light emitting diode, a CRT, etc. Alternatively, it may be performed through an OFT (optical fiber tube) or the like. [Heat Development] Development in the present invention is carried out by heat development, and any method applicable to ordinary heat-developable photographic materials can be used for this heat development. For example, contact with a heated plate, contact with a heated roller or drum, passage through a high temperature atmosphere, use of high frequency heating, or even provision of a conductive layer in the photosensitive element to conduct electricity. It is also possible to utilize Joule heat generated by a strong magnetic field.
There are no particular restrictions on the heating pattern in thermal development, including methods of preheating and then reheating, and methods of heating at high temperatures for short periods of time.
Alternatively, it is possible to continuously raise, lower, or repeat heating at a low temperature for a long time, or even to heat discontinuously, but a simple pattern is preferable. Usually, the developing temperature is 80℃~200℃, and the developing time is 1 second~10
A range of minutes is preferred. For heat development, a commercially available heat development machine can also be used. For example, “Image forming 4634 type”
(Sony Tektronix), "Tyberrot Permodule 277" (3M), "Video Hard Copy Unit NWZ-301" (Japan Radio Co., Ltd.), etc. At least a portion of the imagewise distribution of the thermally transferable dye provided by the dye is transferred to the image-receiving element by heat during thermal development or reheating. [Image-receiving element additive] In the present invention, the image-receiving element is may contain various additives, such as titanium white, silica, acid clay, heavy or light calcium carbonate, etc., in the image-receiving element to improve transfer efficiency or facilitate peeling. , talc, kaolin, natural or synthetic silicates, aluminum hydroxide, zinc oxide, etc. The image receiving element may be integrated with the photosensitive element, or the image receiving element may be integrated with the photosensitive element. It may be in any form that can be separated from the 4-hydroxybenzotriazole silver salt, and may be in any conventionally known form. [Examples] Examples of the present invention are shown below. <Preparation of 4-hydroxybenzotriazole silver salt> 34.0 g of silver nitrate It was dissolved in 450 c.c. of water, and aqueous ammonia was added dropwise while stirring, and the dropping was completed when the formed silver oxide was completely dissolved. 4-Hydroxybenzotriazole Synthesis) 27.5g was dissolved in 350ml of ethanol, and the above ammoniacal silver nitrate solution was added to the mixture.The reaction solution was filtered, washed with water and methanol, and dried to obtain 46.4g of white crystals.Example 1 4 -To 7.26 g of hydroxybenzotriazole silver, 24 ml of a water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd., ESLETSUKU W-201), 116 ml of water, and 70 ml of methanol were added, and the mixture was ground and dispersed in an alumina pole mill to obtain a silver salt dispersion. To 25 ml of this silver salt dispersion were added 0.21 g of phthalic acid, 0.16 g of phthalazine, 0.93 g of exemplary dye-providing substance (1), 0.42 g of the following reducing agent, 5 ml of a 25% aqueous solution of water-soluble polyvinyl butyral, 10 ml of water, Furthermore, the average particle size
Add 36mg of 0.04μ silver iodide emulsion in terms of silver,
A photosensitive element was prepared by applying it to a photographic baryta paper using a wire paper so that the wet film thickness was 55 μm. At this time, 5.8 mg of the reducing agent was applied per 100 cm ² . On the other hand, an image-receiving element was prepared by coating a saturated polyester layer (image-receiving layer) with a dry film thickness of 6 μm on baryta paper, and a photographic material to be combined with the photosensitive element was prepared. This was designated as sample 1. On the other hand, 0.2 g of guanidine trichloroacetic acid was added as a dye release aid to the photosensitive layer of Sample 1.
It was created. Further, when preparing the image-receiving layer of Sample 1, guanidine trichloroacetic acid was added to prepare Sample 3. In addition, the reducing agent was removed from the photosensitive layer of sample 1, and the reducing agent and dye release aid were added to the image-receiving layer.
It was created. The photosensitive layer of the photosensitive element of each sample obtained by drying was exposed to 30,000 CMS through a step wedge. The coated surface of each of the exposed photosensitive layers is brought into close contact with the image receiving layer of each of the image receiving elements, and the surface temperature is increased.
After pressing and heating with an iron at 150°C for 30 seconds, the photosensitive element and image receiving element were peeled off. Separately, each sample was stored for 24 hours under forced deterioration conditions of 50° C. and 70% relative humidity, then exposed and thermally developed as described above, and the image transferred to the image-receiving layer was measured. These results are shown in Table 1 below.

[Table] As is clear from Table 1, the transferred image of Sample 3 according to the present invention has excellent maximum and minimum absorption densities, has little performance deterioration due to strong deterioration, and also has a reducing agent in the image-receiving layer of the present invention. It can be seen that sample 4 containing the dye release aid of the present invention has further improved storage stability over time. Example 2 Silver behenate 4.5g, toluene 20ml, acetone 20ml
ml and 3.2 g of polyvinyl butyral were added, and Dispersion-1 was prepared using an ultrasonic homogenizer. Behenic acid dispersion 2 was obtained by heating and dissolving 3.4 g of behenic acid in 40 ml of an 8% by weight polyvinyl butyral acetone solution and stirring under ice cooling. On the other hand, 0.20 g of phthalic acid, 0.13 g of phthalazine, and 1.55 g of the following reducing agent, exemplary dye-donating substance (36),
0.92g, triethylamine as dye release aid
1.0 g was dissolved in 40 ml of an 8% by weight polyvinyl butyral acetone solution to obtain Solution-1. Further, silver trifluoroacetate and lithium bromide were reacted in a 10% by weight polyvinyl butyral acetone solution to obtain Emulsion-1. 10 ml of the above [Dispersion liquid-1] and 10 ml of [Dispersion liquid-2]
0.3 ml of a 0.05% by weight methanol solution of the following sensitizing dye and 20 mg of mercuric acetate were added thereto. Finally, Solution 1 was added and coated onto a transparent polyester film using a wire bar to a wet film thickness of 74 μm to form a photosensitive layer. A white reflective layer and an image-receiving layer having the following compositions were provided thereon, and another transparent polyimide film was adhered onto the image-receiving layer to prepare sample 5 for comparison. <White reflective layer> (Unit: g/m ² ) Titanium dioxide (average particle size: 1.5μ) 15 Cellulose diacetate 1.2 Sodium dodecyl sulfate 0.08 Ethanol 25 Water 30 <Image-receiving layer> (Unit: g/m ² ) Cellulose diacetate 1.6 Ethanol 21 Water 42 On the other hand, Sample 6 was prepared in exactly the same manner as Sample 5, except that the reducing agent was removed from the photosensitive layer of Sample 5, and the image receiving layer was prepared by dissolving 1.55 g of this reducing agent in the ethanol used for preparing the image receiving layer. It was created. Further, sample 7 was prepared by removing triethylamine from the photosensitive layer of sample 6, dissolving the triethylamine in ethanol, and adding it to the image-receiving layer. Each of these samples was subjected to a forced deterioration test in exactly the same manner as in Example 1, exposed to light, and thermally developed, and the evaluation results are shown in Table 2.

[Table] As is clear from Table 2, Sample 7 according to the present invention maintains excellent performance even after forced deterioration. Example 3 In Example-1, the reducing agent was 0.8 g as shown below.
Dye-donor substances (94) also exemplify dye-donor substances.
Sample 8 was prepared in the same manner as Sample 1 except that 0.5 g of o-phenylphenol was added as a diffusion aid to the photosensitive layer instead of 1.5 g.
Sample 9 was prepared in correspondence with Sample 2, Sample 10 was prepared in correspondence with Sample 3, and Sample 11 was prepared in correspondence with Sample 4. After performing the same forced deterioration test as in Example-1, exposure and heat development were performed. Comparative samples 8 and 9 showed significant performance deterioration, while inventive sample 10 and No. 11, almost no performance deterioration was observed. Example 4 In Example-2, Sample 7 was an integrated type of photosensitive layer and image-receiving layer, so in this example, an image-receiving layer and a white reflective layer with exactly the same content as in Example-2 were placed on a transparent polyimide film base. Sample 12 was prepared by separately preparing an image-receiving element provided with the above and a photosensitive layer having exactly the same content as in Example-2. Therefore, the samples 12 are stacked during thermal development and remain stacked thereafter, and the transferred images are observed through the transparent polyimide film base. Samples 7 and 12 were subjected to forced deterioration tests for 24 hours, 48 hours, and 72 hours under conditions of 50°C and 70% relative humidity. The results are shown in Table 3.

[Table] As is clear from Table 3, the present invention shows good performance whether the photosensitive element and the image receiving element are integrated or separate, but the integrated type (sample 7) is better than the integrated type (sample 7).
It can be seen that 12) has better long-term storage stability.

Claims (1)

[Claims] 1. A heat-developable photosensitive element having a photographic constituent layer containing an organic silver salt and a heat-transferable dye-providing substance, and an image-receiving layer capable of receiving a heat-transferable dye provided from the heat-transferable dye-providing substance by heat development. A heat-developable color photographic material having an image receiving element,
A heat-developable color photographic material characterized in that the image-receiving element contains a dye-releasing aid which is a base or a base-releasing agent.