JPH0140972B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming color images by thermal development. The present invention particularly includes:
In a heat-developable color photosensitive material containing a dye-donating substance that releases a hydrophilic diffusible dye upon heat development, the dye released by heat development is diffusely transferred to a support having a mordant layer to produce a color image. It's about a new way to get. Photography using silver halide has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography.
It has traditionally been the most widely used. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer to a dry processing using heating, etc. It has been. Heat-developable photosensitive materials are well known in the art, and the heat-developable photosensitive materials and their processes are described in U.S. Pat.
No. 3457075, British Patent No. 1131108, No. 1167777
issue and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17029). For information on how to obtain a color image,
Many methods have been proposed. Regarding the method of forming a color image by combining an oxidized form of a developer with a coupler, U.S. Pat.
-Aminophenol-based reducing agent received Belgian patent no.
Issue 802519 and Research Disclosure Magazine
On pages 31 and 32 of the September 1975 issue, sulfonamide phenolic reducing agents were also disclosed in U.S. Patent No. 4021240.
In this issue, sulfonamide phenolic reducing agents and 4
Combinations with equivalent couplers have been proposed. However, in such a method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the color image becomes cloudy. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer. In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue 54.
Described on page 58 RD-1966. With this method, it is difficult to suppress the release of dye in areas not exposed to light, and a clear image cannot be obtained, so it is not a common method. Also, regarding the method of forming positive color images by silver dye bleaching method using heat development, see, for example, the April 1976 issue of Research Disclosure Magazine.
Pages 30-32 (RD-14433), December 1976 issue of the magazine
Pages 14-15 (RD-15227), U.S. Patent No.
Useful dyes and bleaching methods are described in publications such as No. 4235957. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color images may coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver and the like. Further, regarding the method of forming color images using leuco dyes, for example, US Pat. No. 3,985,565,
No. 4022617. However, this method has the disadvantage that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. The present invention provides a new method for forming color images by thermal development and solves the drawbacks of hitherto known materials. That is, an object of the present invention is to provide a new image forming method in which a color image is obtained by thermally transferring a hydrophilic dye released by thermal development to an image receiving material containing a mordant. An object of the present invention is to provide a method for obtaining clear color images using a simple method. An object of the present invention is to provide a method for obtaining color images that are stable over a long period of time. These purposes are achieved by disposing on a support at least a photosensitive silver halide, a hydrophilic binder, a dye release aid, and a compound represented by the following general formula () that is reducible to silver halide and releases a hydrophilic dye. A heat-developable color photosensitive material containing a dye-providing substance, characterized in that the photosensitive silver halide is a silver halide that exhibits an X-ray pattern of silver iodide crystals when measured by X-ray diffraction. This was achieved using a heat-developable color photosensitive material. General formula () R-SO ₂ -D (In the formula, R represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye portion having a hydrophilic group.) Thermal development of the present invention Color photosensitive materials can be used to create a negative version of the original by simply performing thermal development after image exposure.
It is possible to simultaneously provide a silver image having a positive relationship and a diffusible dye in the area corresponding to the silver image. That is, when the heat-developable color photosensitive material of the present invention is imagewise exposed and heat-developed, an oxidation-reduction reaction occurs between the exposed photosensitive silver halide and the reducing dye-donating substance, and a silver image is formed in the exposed area. . In this step, the dye-donating substance is oxidized by silver halide to become an oxidant. This oxidant is cleaved in the presence of a dye release aid, resulting in the release of a hydrophilic, diffusible dye. Therefore, a silver image and a diffusible dye are obtained in the exposed area, and a color image is obtained by transferring the diffusible dye. All reactions that release the diffusible dyes of the present invention are conducted in dry films at elevated temperatures. This release reaction of the diffusible dye is thought to be caused by attack by a so-called nucleophile, and is usually carried out in a liquid.
In the present invention, although it depends on the type of dye-providing compound, the compounds cited as preferred examples showed a high reaction rate even in a dry film. This high response rate is an unexpected finding. Further, the dye-donating compound of the present invention can undergo a redox reaction with silver halide without the aid of a so-called auxiliary developer. This is an unexpected result based on previous findings at temperatures around room temperature. The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention is represented by the following general formula R-SO ₂ -D (). Here, R represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye portion having a hydrophilic group. The reducing substrate in the dye-donating substance R-SO ₂ -D has a redox potential of 1.2 V or less with respect to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte. Something is preferable. Preferred reducing substrates have the following general formulas () to (). Here, R ¹ and R ² are each a hydrogen atom, an alkyl group,
Cycloalkyl group, aryl group, alkoxy group,
Aryloxy group, aralkyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N-substituted carbamoyl group, N-substituted sulfamoyl group, halogen atom, alkylthio group, Represents a group selected from arylthio groups, and the alkyl and aryl groups in these groups further include alkoxy groups, halogen atoms, hydroxyl groups, cyano groups, acyl groups, acylamino groups, substituted carbamoyl groups, substituted sulfamoyl groups, It may be substituted with an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group, or a carbalkoxy group. Furthermore, the hydroxyl group and amino group in R may be protected with a protecting group that can be regenerated by the action of a nucleophilic reagent. The properties required of the reducing substrate R include the following. 1. To be rapidly oxidized by silver halide and to efficiently release a diffusible dye for image formation through the action of a dye release aid. 2. The dye-donating substance must be immobilized in a hydrophilic or hydrophobic binder, and only the released dye must have diffusibility. Therefore, the reducing substrate R must have large hydrophobicity. 3. Excellent stability against heat and dye release aids, and should not release image-forming dyes until oxidized. 4. Easy to synthesize. Next, preferred specific examples of R that satisfy these conditions will be shown. In the examples, NH- represents a linkage with the dye moiety. Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes, and representative examples are shown for each dye. In addition,
These dyes can also be used in a temporarily short-waveformed form that can be restored during development.

【formula】

【formula】 【formula】

【formula】 In the above formula, R ₁₁ to _{R 16} are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group, an alkylsulfonylamino group, Arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N- It represents a substituent selected from a substituted carbamoyl group, an acyloxyalkyl group, an amino group, a substituted amino group, an alkylthio group, and an arylthio group, and the alkyl group and aryl group moiety in these substituents further include a halogen atom,
hydroxyl group, cyano group, acyl group, acylamino group,
It may be substituted with an alkoxy group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or a ureido group. Hydrophilic groups include hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, imide group, hydroxamic acid group, quaternary ammonium group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, sulfamoylamino group, substituted Examples include a sulfamoylamino group, a ureido group, a substituted ureido group, an alkoxy group, a hydroxyalkoxy group, and an alkoxyalkoxy group. In the present invention, those whose hydrophilicity is significantly increased by proton dissociation under basic conditions are particularly preferred (PKa<12), and these include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, and imide groups. , a hydroxamic acid group, a (substituted) sulfamoyl group, a (substituted) sulfamoylamino group, and the like. The characteristics required for image-forming dyes are (1) having a hue for color reproduction, (2) having a large molecular extinction coefficient, and (3) being sensitive to light, heat, and a dye release aid contained in the system. Examples include stability against other additives, and (4) ease of synthesis. Specific examples of preferred image-forming dyes satisfying these conditions are shown below. Here, H ₂ N—SO ₂ represents a bonding site with a reducing substrate. Next, specific examples of preferred dye-providing substances will be shown. Next, the method for synthesizing the dye-donating substance will be described. Generally, the dye-donating substance of the present invention is a reducing substrate R
It can be obtained by condensing the amino group of and the chlorosulfonyl group of the image-forming dye. The amino group of the reducing substrate R can be introduced by reduction of nitro, nitroso, or azo groups or by ring opening of benzoxazole depending on the type of substrate, and can be used as a free base or as a salt of an inorganic acid. . On the other hand, the chlorosulfonyl group in the image-forming dye moiety can be derived from the sulfonic acid or sulfonate of the dye by a conventional method, ie, by the action of a chlorinating agent such as phosphorus oxychloride, phosphorus pentachloride, or thionyl chloride. The condensation reaction between the reducing substrate R and the image-forming dye part D is generally carried out in an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, etc. using pyridine, picoline, lutidine, triethylamine, It can be carried out in the presence of an organic base such as diisopropylethylamine at a temperature of 0 to 50°C, and the desired dye-donating substance can usually be obtained in a very good yield. An example of its synthesis is shown below. Synthesis Example 1 Synthesis of 6-hydroxy-2-methylbenzoxazole 2,4-dihydroxyacetophenone 306g,
164 g of hydroxylamine hydrochloride, 328 g of sodium acetate, 1000 ml of ethanol, and 500 ml of water were mixed and heated under reflux for 4 hours. The reaction solution was poured into 10 g of water, and the precipitated crystals were collected to obtain 314 g of 2,4-dihydroxyacetophenone oxime. Dissolve 30g of this oxime in 400ml of acetic acid and heat to 120°C.
Hydrogen chloride gas was blown into the mixture for 2 hours while heating and stirring. After cooling, the precipitated crystals were collected and washed with water to obtain 17 g of 6-hydroxy-2-methylbenzoxazole. Synthesis Example 2 Synthesis of 6-hexadecyloxy-2-methylbenzoxazole 18.0 g of 6-hydroxy-2-methylbenzoxazole synthesized in Synthesis Example 1, 36.6 g of 1-bromohexadecane, 24.0 g of potassium carbonate, N,N- 120 ml of dimethylformamide was stirred at 90°C for 4 to 5 hours. The solid was separated from the reaction solution, and the solution was poured into 500 ml of methanol. Take the precipitated crystals,
45.0 g of 6-hexadecyloxy-2-methylbenzoxazole was obtained. Synthesis Example 3 Synthesis of 2-acetylamino-5-hexadecyloxyphenol 6-hexadecyloxy-2- obtained in Synthesis Example 2
Methylbenzoxazole 111g, ethanol
Mix 1300ml, 33% hydrochloric acid 110ml, and 550ml water, 55~
The mixture was stirred at 60°C for 4 hours. After cooling, the precipitated crystals were collected to obtain 113 g of 2-acetylamino-5-hexadecyloxyphenol. Synthesis Example 4 Synthesis of 2-acetylamino-4-t-butyl-5-hexadecyloxyphenol 30.0 g of 2-acetylamino-5-hexadecyloxyphenol obtained in Synthesis Example 3, Amberlyst 15 (Rohm, USA) & Haas Inc. registered trademark)
20.0 g and 300 ml of toluene were mixed, and while stirring and heating at 80 to 90°C, isobutene was blown into the mixture for 5 hours. After separating the solid, the liquid was concentrated, and 350 ml of n-hexane was added to the residue to precipitate crystals.
23.5 g of 2-acetylamino-4-t-butyl-5-hexadecyloxyphenol was obtained. Synthesis Example 5 Synthesis of 2-amino-4-t-butyl-5-hexadecyloxyphenol 2-acetylamino-4-t- obtained in Synthesis Example 4
Butyl-5-hexadecyloxyphenol 23.0
g, 120 ml of ethanol, and 96 ml of 35% hydrochloric acid,
The mixture was stirred and refluxed for 5 hours. After cooling the reaction solution, the precipitated crystals were collected to obtain 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride.
23.2g was obtained. Synthesis example 6 4-t-butyl-5-hexadecyloxy-2
-Synthesis of [2-(2-methoxyethoxy)-5-nitrobenzenesulfonylamino]phenol 2-amino-4-t-butyl- obtained in Synthesis Example 5
5-hexadecyloxyphenol hydrochloride 4.4g
and 3.1 g of 2-(2-methoxyethoxy)-5-nitrobenzenesulfonyl chloride in N,N-
Pyridine dissolved in 12 ml of dimethylacetamide
After adding 2.5 ml, the mixture was stirred at 25°C for 1 hour. When the reaction solution was poured into dilute hydrochloric acid, an oily substance precipitated. When 30 ml of methanol was added to this oil, it crystallized and was collected. Yield 4.5g Synthesis Example 7 Synthesis of 2-[5-amino-2-(2-methoxyethoxy)benzenesulfonylamino]-4-t-butyl-5-hexadecyloxyphenol 10g of the compound obtained in Synthesis Example 6 above ethanol 60
Approximately 0.5 g of 10% palladium-carbon catalyst dissolved in ml
After adding hydrogen, pressurize hydrogen to 55Kg/cm ² and
Stirred at ℃ for 6 hours. Next, the catalyst was removed while hot, and when it was allowed to cool, crystals precipitated and were collected. Yield 7.5g. Synthesis Example 8 Synthesis of 3-cyano-4-[4-(2-methoxyethoxy)-5-sulfophenylazo]-1-phenyl-5-pyrazolone Add 5- to a solution of 8.0 g of sodium hydroxide and 200 ml of water.
Add 49.4 g of amino-2-(2-methoxyethoxy)benzenesulfonic acid, and add sodium nitrite.
A 13.8g aqueous solution (50ml) was added. Concentrated hydrochloric acid 60% separately
ml and 400 ml of water was prepared, and the above solution was added dropwise to this at 5°C or below. Thereafter, the reaction was completed by stirring at 5° C. or lower for 30 minutes. Separately, prepare a solution of 16.0 g of sodium hydroxide, 200 ml of water, 33.0 g of sodium acetate, and 200 ml of methanol, add 37.0 g of 3-cyano-1-phenyl-5-pyrazolone, and pour the diazo solution prepared above at 10°C or below. dripped. After the completion of the dropwise addition, the mixture was stirred for 30 minutes at 10° C. or lower, and then for 1 hour at room temperature. The precipitated crystals were collected, washed with 200 ml of acetone, and air-dried. Yield 52.0gm.p.263-265℃ Synthesis Example 9 3-cyano-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-
Synthesis of 1-phenyl-5-pyrazolone 3-cyano-4-[(4-
Methoxyethoxy-5-sulfophenylazo]-
1-phenyl-5-pyrazolone 51.0g, acetone
N,
50 ml of N-dimethylacetamide was added dropwise at below 50°C. After the addition, the mixture was stirred for about 1 hour and gradually poured into ice water. After separating the precipitated crystals, they were washed with 100 ml of acetonitrile and air-dried. Yield 46.7gm.p.181-183℃ Synthesis Example 10 Synthesis of dye-donating substance (1) 2-[5-amino-2-(2-
methoxyethoxy)benzenesulfonylamino-
6.3 g of 4-t-butyl-5-hexadecyloxyphenol and 30 ml of N,N-dimethylacetamide
3-cyano-4-[4 obtained in Synthesis Example 9]
4.6 g of -(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-1-phenyl-5-pyrazolone was added, followed by 5 ml of pyridine.
After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. N,N-dimethylacetamide - 7.5g recrystallized from methanol
I got it. mp189～191℃ Synthesis Example 11 Synthesis of dye-donating substance (2) 2-[5-amino-2-(2-
methoxyethoxy)benzenesulfonylamino-
6.3 g of 4-t-butyl-5-hexadecyloxyphenol and 30 ml of N,N-dimethylacetamide
3-cyano-4-(5-chloro-2-
Methylsulfonylphenylazo)-1-(4-chlorosulfonylphenyl)-5-pyrazolone 5.0
Then, 5 ml of pyridine was added. After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallization from acetonitrile yielded 8.4 g. mp144-149℃ Synthesis Example 12 Synthesis of dye-donating substance (10) 4.4 g of 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride and 4-[3
-chlorosulfonyl-4-(2-methoxyethoxy)phenylazo]-2-(N,N-diethylsulfamoyl)-5-methylsulfonylamino-
6.5 g of 1-naphthol was dissolved in 20 ml of N,N-dimethylacetamide and 4.2 ml of pyridine was added. 1
After stirring at 25°C for an hour, the reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and purified by silica gel column chromatography (eluted with a mixed solvent of chloroform-ethyl acetate (2:1)). Yield: 5.2g. Synthesis Example 13 Synthesis of dye-donating substance (17) Dissolve 11.6 g of 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride in 100 ml of N,N-dimethylacetamide, and add 12 ml of pyridine.
added. To this, 5-(3-chlorosulfonylbenzenesulfonylamino)-2-(Nt-butylsulfamoyl)-4-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthol
Added 20g. After stirring for 1 hour, pour into 500ml of ice water.
The precipitate was recrystallized from isopropyl alcohol-acetonitrile (1:1) to obtain 6.8 g. Synthesis example 14 Synthesis of dye-donating substance (19) 2-[5-amino-2-(2-methoxyethoxy)benzenesulfonylamino]-4-t-butyl-5-hexadecyloxyphenol 31.5 g,
Dissolve 39.1 g of 5-(3-chlorosulfonylbenzenesulfonylamino)-4-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthol in 100 ml of N,N-dimethylacetamide,
21 ml of pyridine was added. After stirring for 80 minutes, methanol
250ml and 100ml of water were added. The precipitated resinous material solidified after a while and was removed. This was recrystallized from a toluene-methanol-water (16:4:3) mixed system to obtain 41.5 g. The reducible dye-donating substance that releases the diffusible dye of the present invention can be used within a certain concentration range. A generally useful concentration range is from about 0.01 mole to about 4 moles of dye-providing material per mole of silver halide. Concentrations particularly useful in the present invention range from about 0.03 mol to 1 mol of silver halide.
It is about 1 mole. In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary developer, which is oxidized by silver halide and its oxidized product has the ability to oxidize the reducing substrate R in the dye-donating substance. Useful auxiliary developers include hydroquinone, alkyl-substituted hydroquinones such as tertiary-butylhydroquinone and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkyl-substituted hydroquinones such as methoxyhydroquinone. substituted hydroquinones,
There are polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives,
Hydroxylamines such as N,N′-di-(2-ethoxyethyl)hydroxylamine, pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, Reductones and hydroxytetronic acids are useful. Auxiliary developers can be used in a range of concentrations. Useful concentration range is 0.01 for silver halide
A particularly useful concentration range is from 0.1 times molar to 4 times molar. In the present invention, in addition to silver halide, an organic silver salt oxidizing agent can be present in an amount of up to 0.2 mol per mol of silver halide. As the organic silver salt oxidizing agent, those described in Japanese Patent Application No. 56-157798 can be used. Particularly preferred silver halides in the present invention are:
Some of the grains contain silver iodide crystals. That is, it is particularly preferable that a pattern of pure silver iodide appears when the silver halide is subjected to X-ray diffraction. Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary silver halide emulsions, complete mixed crystals of silver halide grains are formed. For example, when X-ray diffraction of the grains of a silver iodobromide emulsion is measured, patterns of silver iodide crystals and silver bromide crystals do not appear, but an X-ray pattern appears at a position corresponding to a mixing ratio between the two. Particularly preferred silver halides in the present application include silver chloroiodide, silver iodobromide, which contain silver iodide crystals in their grains, and therefore exhibit an X-ray pattern of silver iodide crystals.
Silver chloroiodobromide. Such silver halide, for example, silver iodobromide, can be obtained by first adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide. Silver halide grain size is from 0.001μm to 2μm
and preferably from 0.001 μm to 1 μm. The silver halide used in the present invention may be used as it is, but it may also be compounded with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, gold, platinum, palladium, rhodium or iridium, and tin halide. Chemical sensitization may be achieved by the use of reducing agents such as or combinations thereof. For more information, see “The
Theory of the Photographic Process” 4th edition,
TH James, Chapter 5, pages 149-169. The silver halide and the dye-providing substance may be present in the same layer, or a layer containing silver halide may be provided on the layer containing the dye-providing substance. Although the thermal development process during heating of the present invention is not fully understood, it can be considered as follows. When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. Regarding this,
“The Theory of the
Photographic Process” 3rd Edition page 105~
It is described on page 148. By heating the photosensitive material, the reducing agent, in the case of the present invention, the dye-donating substance, with the help of the alkaline agent released by heating, uses the latent image nucleus as a catalyst to reduce the silver halide, thereby converting silver or metal. produced and itself oxidized. A nucleophilic reagent (dye release aid in the present invention) attacks this oxidized dye-donating substance, and the dye is released. In the present invention, the coating amount of photosensitive silver halide is suitably 50 mg to 10 g/m ² in total in terms of silver. The photosensitive silver halide of the present invention is prepared in the following binder. A dye-providing substance is also dispersed in the binder described below. The binders used in the present invention can be contained alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes. Various dye release aids can be used in the heat-developable color photosensitive material of the present invention. A dye-releasing agent is one that can nucleophilically attack a dye-donating substance oxidized by silver halide and release a diffusible dye. 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 silver halide and the dye-donating substance. 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]methane. U.S. Pat. No. 2,410,644 describes tetramethylammonium betaine 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, and 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 described in Japanese Patent Publication No. 88386/1986.
NH ₄ Fe(SO ₄ ) ₂ ·/2H ₂ O and the like 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. Further, in the heat-developable color light-sensitive material of the present invention, a compound which activates development and simultaneously stabilizes the image can be used. Therein, U.S. Patent No. 3301678
Isothiuroniums represented by 2-hydroxyethyl isothiuronium and trichloroacetate described in No. 1, 1 and 8 described in U.S. Patent No. 3,669,670
- Bisisothiuriums such as (3,6-dioxaoctane)bis(isothiuronium trifluoroacetate), thiol compounds described in West German Patent No. 2162714, 2-amino-2 described in U.S. Patent No. 4012260 -thiazolium trichloroacetate, 2-amino-5-bromoethyl-2
- Thiazolium compounds such as thiazolium trichloroacetate, bis(2-amino-2-thiazolium) methylene bis(sulfonylacetate), 2-amino- described in US Pat. No. 4,060,420
Compounds having α-sulfonylacetate as an acidic moiety such as 2-thiazolium phenylsulfonylacetate, compounds having 2-carboxycarboxamide as an acidic moiety as described in US Pat. No. 4,088,496, etc. are preferably used. . These compounds or mixtures can be used in a wide variety of ways. 1/100 molar ratio to silver
It is preferably used in a range of 10 times to 10 times, particularly 1/20 to 2 times. The heat-developable color photosensitive material of the present invention can contain a heat solvent. As used herein, a "thermal solvent" 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 of polyethylene oxide such as oleate ester, beeswax, monostearin, -SO ₂
-, -CO--containing high dielectric constant compounds, 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 described in Research Disclosure Magazine, December 1976 issue, pages 26-28, methyl anisate, biphenyl suberate, etc. are preferred. used. In the case of the present invention, the dye-providing substance is colored, and although it is not so necessary to incorporate an anti-irradiation or anti-halation substance or dye into the light-sensitive material, in order to further improve the sharpness, 48-3692, U.S. Patent No. 3253921,
Filter dyes and absorbent substances described in specifications such as No. 2527583 and No. 2956879 can be contained. Preferably, these dyes are thermally decolorizable, such as those described in U.S. Pat. No. 3,769,019, U.S. Pat.
Dyes such as those described in No. 3,615,432 are preferred. The photosensitive material according to the present invention may contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer,
It can contain an intermediate layer, an AH layer, a peeling layer, etc. For various additives, “Research
Additives described in No. 17029 of June 1978 such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, There are anti-fading agents, etc. Similar to the heat-developable photosensitive layer according to the present invention, protective layers, intermediate layers, undercoat layers, back layers and other layers also include
The respective coating solutions are prepared and applied sequentially onto a support by various coating methods such as dipping, air knife, curtain coating, or hopper coating as described in U.S. Pat. No. 3,681,294, and then dried. You can make materials. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. Various exposure means can be used for the heat-developable photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources. The original drawing may be a line image such as a technical 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 drawing may be done by overlaying the original drawing by contact printing, 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 send the image to a CRT or FOT, form the image on a heat-developable 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 play a color image,
Three types of LEDs that emit exposure light, red light, and infrared light may be used, and the parts of the sensitive material that are sensitive to these lights may be designed to emit yellow, magenta, and cyan dyes, respectively. That is, the green-sensitive portion (layer) may contain a yellow dye-providing substance, and the red-sensitive portion (layer) may contain a magenta dye-providing substance. Other combinations are also possible as required. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light-receiving element such as a CCD and storing it in the memory of a computer, processing this information as necessary and performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source. There is also a method of directly emitting light from three types of LEDs for exposure based on the processed information. After exposure of a heat-developable color photographic element, the resulting latent image is e.g.
Development can be accomplished by heating the element in its entirety at a moderately elevated temperature, such as for 300 seconds. As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. A temperature range of about 110°C to about 160°C is particularly useful. The heating means may be simply a hot plate, an iron, a hot roller or the like. In the present invention, a specific method for forming a good color image by thermal development is thermal diffusion transfer of a hydrophilic diffusible dye. For this purpose, a heat-developable color photosensitive material has a photosensitive layer (layer) on a support that contains at least silver halide, a dye-providing substance that is also a reducing agent for silver halide, a hydrophilic binder, and a dye release aid.
and an image-receiving layer ( ) that can receive the hydrophilic and diffusible dye formed by the layer ( ). The above-mentioned photosensitive layer () and image-receiving layer () may be formed on the same support, or may be formed on separate supports. The image-receiving layer () can also be peeled off from the photosensitive layer (). For example, after imagewise exposure of a heat-developable color light-sensitive material, uniform heat development can be performed, and then the image-receiving layer can be peeled off. In another specific method, after imagewise exposure, an image-receiving layer (2) may be superimposed on a photosensitive layer (2) that has been uniformly heat-developed, and the dye may be transferred at a temperature lower than the development temperature. In this case, "lower than the developing temperature" means
It includes room temperature, and preferably refers to a temperature from room temperature to about 40°C or more lower than the heat development temperature. For example, this corresponds to a heat development temperature of 120°C and a transfer temperature of 80°C. There is also a method in which only the photosensitive layer () is imagewise exposed, and then the image-receiving layer () is overlaid and uniformly developed by heating. The image receiving layer () contains a dye mordant. Various mordants can be used in the present invention, and a useful mordant can be selected depending on the physical properties of the dye, transfer conditions, other components contained in the photographic material, etc. The mordant used in the present invention is a high molecular weight polymeric mordant. The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and have a molecular weight of 5,000 to 200,000, particularly 10,000 to 10,000. 50,000. For example, US Patent No. 2548564, US Patent No. 2484430, US Patent No.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Patent Nos. 3148061 and 3756814;
Polymer mordants capable of crosslinking with gelatin, etc., disclosed in U.S. Pat.
No. 2798063, Japanese Unexamined Patent Publication No. 115228, No. 54-
Aqueous sol-type mordant disclosed in No. 145529, No. 54-126027, etc.; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088; U.S. patent
A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification of No. 4168976 (Japanese Unexamined Patent Publication No. 54-137333); furthermore, US Pat. No. 3709690, US Pat. Same No. 3557066,
No. 3271147, No. 3271148, Japanese Patent Application Publication No. 1971-
No. 71332, No. 53-30328, No. 52-155528, No. 53
Examples include mordants disclosed in Japanese Patent No. 125 and No. 53-1024. Other mordants described in US Pat. No. 2,675,316 and US Pat. No. 2,882,156 can also be mentioned. Among these mordants, those that are difficult to move from the mordant to other layers within the light-sensitive material layer are preferred; for example,
Preferably used are those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants. Particularly preferred polymer mordants are shown below. (1) Groups that have a quaternary ammonium group and can be covalently bonded to gelatin (for example, aldehyde groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups, pyridinium propionyl groups,
Polymers having vinylcarbonyl groups, alkylsulfonoxy groups, etc.) For example, (2) A reaction product of a polymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer, and a crosslinking agent (eg, bisalkanesulfonate, bisarenesulfonate).

[Formula] R ₂₁ : H, alkyl group R ₂₂ : H, alkyl group, aryl group Q : divalent group R ₂₃ , R ₂₄ , R ₂₅ : alkyl group, aryl group, or at least 2 of R ₂₃ to _{R 25} may be combined to form a heterocycle. X: Anion (the above alkyl groups and aryl groups include substituted ones) (3) Polymer represented by the following general formula x: about 0.25 to about 5 mol% y: about 0 to about 90 mol% z: about 10 to about 99 mol% A: Monomer having at least two ethylenically unsaturated bonds B: Copolymerizable ethylenically unsaturated Monomer Q: N, P R ₃₁ , R ₃₂ , R ₃₃ : Alkyl group, cyclic hydrocarbon group, or at least two of R ₃₁ to _{R 33} may be combined to form a ring. (These groups and rings may be substituted.) (4) Copolymer consisting of (a), (b) and (c) (a) X: Hydrogen atom, alkyl group, or halogen atom (alkyl group may be substituted) (b) Acrylic acid ester (c) Acrylonitrile (5) 1/3 of the repeating unit represented by the following general formula
Water-insoluble polymer having more than R ₄₁ , R ₄₂ , R ₄₃ : Each represents an alkyl group, and the total number of carbon atoms in R ₄₁ to _{R 43} is 12 or more. (The alkyl group may be substituted.) X: Anion (6) Polymer having repeating units represented by (d) and/or (e) below (d)

【formula】 (e)

[Formula] Z: atoms necessary to complete the nitrogen-containing heterocycle R ₅₁ and R ₅₂ : H alkyl, hydroxyalkyl,
^Aralkyl For example, it is also possible to use gelatin manufactured by different methods such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment. The mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. However, the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is 0.5
Preferably, it is used at ~8 g/ ^m2 . The image receiving layer ( ) may have a white reflective layer. For example, on top of a mordant layer on a transparent support,
A layer of titanium dioxide dispersed in gelatin can be created. The titanium dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained. A typical image-receiving material for diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a transparent support. A transfer solvent can be used to transfer the dye from the photosensitive layer to the image-receiving layer. As the transfer solvent, water and a basic aqueous solution containing sodium chloride, potassium hydroxide, and an inorganic alkali metal salt are used. Further, low-boiling point solvents such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, and mixed solutions of these low-boiling point solvents and water or basic aqueous solutions are used. The transfer solvent may be used by moistening the image-receiving layer with the solvent, or may be incorporated into the material as crystal water or microcapsules. Example 1 40 g of gelatin and 26 g of KBr are dissolved in 3000 ml of water. The solution is kept at 50°C and stirred. Then silver nitrate
A solution of 34 g dissolved in 200 ml of water is added to the above solution over a period of 10 minutes. Then, a solution of 3.3 g of KI dissolved in 100 ml of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus prepared is adjusted, and excess salt is removed by sedimentation. Thereafter, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g. When X-ray diffraction of the grains of this silver iodobromide emulsion was measured, it showed an X-ray diffraction pattern of silver iodide crystals. Next, we will describe how to make a gelatin dispersion of a dye-donating substance. 10g of dye-donating substance (10) as a surfactant,
Weigh 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 20 g of tricresyl phosphate (TCP), add 30 ml of ethyl acetate, and dissolve by heating to approximately 60°C to form a homogeneous solution.
After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, use a homogenizer for 10 minutes.
Disperses at 10000RPM. This dispersion liquid is called a dispersion of a dye-providing substance. Next, a method for preparing a photosensitive coating will be described. (a) Photosensitive silver iodobromide emulsion 5 g (b) Dispersion of dye-providing substance 3.5 g (c) A solution of 400 mg of guanidine trichloroacetic acid dissolved in 4 ml of ethanol Mix the above (a) to (c), After heating and dissolving, it was coated on a polyethylene terephthalate film with a thickness of 180 μm to a wet film thickness of 60 μm. After drying this coated sample, it was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 150°C. Next, a method for forming an image-receiving material having an image-receiving layer will be described. 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
100g 10% lime processed gelatin dissolved in 200ml water
mixed evenly. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 20 μm. After drying, this sample was used as an image receiving material. After the image-receiving material was immersed in water, the above-mentioned heated photosensitive material was stacked on top of each other so that the film surfaces were in contact with each other. After 30 seconds, the image-receiving material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the image-receiving material. The density of this negative image was measured using a Macbeth transmission densitometer (TD-504).
When measured using a green light, the maximum density was 2.20 and the minimum was 0.20. In addition, the gradation of the sensitometric curve is a straight line, with an exposure difference of 10
There was a concentration difference of 1.40 times. Examples 2 to 5 Dye-donating substance instead of dye-donating substance (10)
(1) Photosensitive material No. 2 was prepared in the same manner as in Example 1 except that 5 g was used. Similarly, photosensitive materials Nos. 3 to 5 were prepared using 10.5 g of dye-donating substance (2), 10.5 g of dye-donating substance (17), and 11.0 g of dye-donating substance (19), respectively. Using the above photosensitive materials No. 2 to 5, the same treatment as in Example 1 was carried out to obtain a negative color image on the image-receiving material. The measured concentration values for each are shown in the table below.

[Table] Example 6 The same operations and treatments as in Example 1 were performed except that guanidine trichloroacetic acid was not used. As a result, only a slight magenta color image (maximum density 0.18) was obtained. Therefore, we raised the temperature of the heat block to 180℃ and added the photosensitive material to 30℃.
When the film was heated uniformly for a second and the same transfer process as in Example 1 was performed, a negative image with a maximum density of 0.80 and a minimum density of 0.25 was obtained. Example 7 Instead of using guanidine trichloroacetic acid,
The same operations and treatments as in Example 1 were carried out except for using 0.12 g of guanidine acetate. As a result, a negative magenta image was obtained on the image receiving material. The maximum concentration was 1.80 and the minimum concentration was 0.80. Example 8 1 as an auxiliary developer in the photosensitive coating of Example 1
-Phenyl-4-methyl-4-oxymethyl-3
-The same operations and treatments as in Example 1 were carried out except for adding 0.4 g of pyrazolidinone. The density of the resulting magenta color image is 2.40 min.
It was 0.12. This result is almost the same as in Example 1, indicating that the present invention allows sufficient image formation even without the use of an auxiliary developer. Example 9 In the dye transfer process of Example 1, the image receiving material was immersed in a 0.1N sodium hydroxide solution instead of being immersed in water. As a result, a magenta color image having a maximum density of 2.5 and a minimum density of 0.40 was obtained. Example 10 Instead of using guanidine trichloroacetic acid
0.40 g of trichloroacetate of HOC ₂ H ₄ OC ₂ H ₄ NH ₂
Except for the use, the operations and treatments were exactly the same as in Example 1. As a result, a negative magenta image was obtained on the image receiving material. Its maximum concentration is 1.70 and minimum concentration is 0.25
It was hot. Preferred embodiments are as follows. 1 Contains on the support at least a photosensitive silver halide, a hydrophilic binder, a dye release aid, and a dye donating property that is reducible to silver halide and releases a hydrophilic diffusible dye. An image forming method in a heat-developable color photosensitive material, which comprises transferring the released dye to an image-receiving material having a mordant to form a color image. 2. A diffusion transfer type heat-developable color photosensitive material according to the claims, which contains a reducing agent for silver halide, if necessary. 3. A heat-developable color photosensitive material as claimed in the claims, characterized in that it is capable of reducing silver halide and has a dye-providing property that releases a hydrophilic diffusible dye represented by the following general formula (). R--SO ₂ --D () where R represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye. 4. A heat-developable color photosensitive material, characterized in that the reducing substrate R in the dye-donating substance R--SO ₂ --D in item 3 has an oxidation-reduction potential of 1.2 V or less with respect to a saturated calomel electrode. 5. A heat-developable color photosensitive material, characterized in that the reducing substrate R in the dye-donating substance R--SO ₂ --D of item 3 is represented by the following general formulas () to (). Here, R ¹ and R ² are each a hydrogen atom, an alkyl group,
Cycloalkyl group, aryl group, alkoxy group, aryloxy group, aralkyl group, acyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N
-Represents a substituent selected from a substituted carbamoyl group, an N-substituted sulfamoyl group, a halogen atom, an alkylthio group, and an arylthio group, and the alkyl group and aryl group moiety in these substituents further includes an alkoxy group, a halogen atom, hydroxyl group, cyano group, acyl group, acylamino group,
substituted carbamoyl group, substituted sulfamoyl group,
It may be substituted with an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group, or a carbalkoxy group. 6. A patent characterized in that the D portion in the dye-donating substance R-SO ₂ -D in Item 3 is a hydrophilic azo, azomethine, anthraquinone, naphthoquinone, styryl, nitro, quinoline, carbonyl, or phthalocyanine dye. The heat-developable color photosensitive material as claimed. 7. A heat-developable color photosensitive material, wherein the dye-releasing aid as claimed in the claims is a base, a base-releasing agent, or a water-releasing compound. 8. A heat-developable color photosensitive material, wherein the reducing agent according to the claims is capable of oxidizing the reducing substrate R according to the third embodiment. 9. A heat-developable color photosensitive material, wherein the hydrophilic binder in the claims is gelatin or a gelatin derivative. 10. The image forming method according to Embodiment 1, characterized in that the released diffusible dye is transferred to an image-receiving material using water or a basic aqueous solution. 11. An image forming method, characterized in that a transferred image is obtained by using a mordant in the image-receiving material according to Embodiment 10.

Claims (1)

[Claims] 1. At least photosensitive silver halide on a support,
A heat-developable color photosensitive material containing a hydrophilic binder, a dye-releasing aid, and a dye-providing substance represented by the following general formula () that is reducible to silver halide and releases a hydrophilic dye. . A heat-developable color photosensitive material, wherein the photosensitive silver halide is a silver halide that exhibits an X-ray pattern of silver iodide crystals when measured by X-ray diffraction. General formula () R-SO ₂ -D (In the formula, R represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye portion having a hydrophilic group.) 2 On a support at least photosensitive silver halide,
A heat-developable color photosensitive material containing a hydrophilic binder, a dye-releasing aid, and a dye-providing substance represented by the following general formula () that is reducible to silver halide and releases a hydrophilic dye. The heat-developable color photosensitive material, in which the photosensitive silver halide is silver halide that shows an X-ray pattern of silver iodide crystals when measured by X-ray diffraction, is thermally developed after or simultaneously with image exposure and released. A method for forming a color image, comprising transferring the hydrophilic dye to an image-receiving layer. General formula () R-SO ₂ -D (In the formula, R represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye moiety having a hydrophilic group.)