JPS59174834A - Dry type image forming method - Google Patents

Abstract

PURPOSE:To obtain a dry type image high in quality by imagewise exposing photosensitive material contg. photosensitive silver halide, a specified dye donor capable of releasing a mobile dye, etc., heating it, and transferring the produced mobile dye to fixing layer with a hot solvent to fix it to the layer. CONSTITUTION:A photosensitive material is prepared by forming on a support a layer contg. photosensitive silver halide; a hydrophilic binder; an agent for reducing said silver halide, e.g. 4-amino-2,6-dichlorophenol; a dye donor combining with the oxidized product of a reducing agent and releasing a mobile dye, such as a compd. of formula I or II; and a hydrophilic hot solvent, e.g. N- methylurea; and the like. This photosensitive material s imagewise exposed, heat developed, a mobile dye formed in the unexposed areas is transferred in the presence of a hydrophilic hot solvent in a high temp. state, and it is fixed in a dye fixing layer to form an intended dry method image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a completely dry image forming method using a silver halide photosensitive material. More specifically, the present invention relates to a method for fixing a color image obtained by heat development onto a dye-fixing layer by heating, without using a thread containing a solvent.

Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and grain density compared to other photographic methods, such as electrophotography and diazo photography. '
By changing the image forming processing method of the tA material from the conventional M acid treatment using a developer etc. to a dry treatment using heating etc.
Techniques have been developed that allow easy and rapid image acquisition.

Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering J (Published by Corona Publishing, 1979), pp. 553-555, April 1978. Video information 40 Emperor, Ne
bullets Hand-book of Ph
otography and reprography
7th Ed.

(Van No5trand Reinhold C
company) on pages 32 to 33,
U.S. Patent No. 3.152,904, 3°301.67
No. 8, No. 3,392,020, No. 3.457,075
No. 1,131°108, British Patent No. 1,167.
No. 777 and Rigid Disclosure Magazine 19
It is described in the June 1978 issue, pages 9 to 15 (RD-17029).

Many methods have already been proposed for obtaining color images using a dry method. U.S. Pat. No. 3.5 describes a method for forming color images by combining an oxidized developer with a coupler.
No. 31.286, p-phenylene diamine reducing agents and phenolic or active methylene couplers; U.S. Pat. No. 3,761.270, p-aminophenolic reducing agents; and Research Disclosure 1975 September issue 31-32
In US Pat. No. 4,021,240, a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed.

However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem 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 nitrogen-containing heterocyclic group is introduced into the dye to form a silver salt,
A method of making dyes Mm by heat development is described in Research Disclosure magazine, May 1978 issue, pages 54-58 (R
D-16966). This method is not a common method because it is difficult to suppress the release of dye in areas not exposed to light, making it impossible to obtain clear images.

Regarding the method of forming positive color images by heat-sensitive silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433).
), December 1976 issue of the same magazine, pages 14-15 (RD-1
5227) and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

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 image is gradually reduced by coexisting free silver, etc. Since it is bleached, it has the disadvantage of not being able to withstand long-term storage.

Further, methods for forming color images using leuco dyes are described in, for example, U.S. Pat. Nos. 3,985,565 and 4.
No. 022,617. 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 inventors have already provided a new photosensitive material capable of solving the drawbacks of these conventional methods, and provided an image forming method therefor (Japanese Patent Application No. 56-177-611).

This is a photosensitive material that can release a mobile hydrophilic dye by a simple method of heating in a substantially water-free state, and this mobile dye is mainly supplied externally with a dye transfer solvent. , relates to an image forming method characterized by transferring the dye to a fixing layer.

As a result of further research into the above-mentioned invention, the present inventors have discovered that, by simply heating, images of movable dyes can be formed by heating in a state substantially free of water. , they have discovered that it can be easily moved, and have arrived at the present invention.

Therefore, a first object of the present invention is to provide a simple method for fixing a hydrophilic color S image produced by heat development performed after or simultaneously with exposure to a dye fixing layer.

A second object of the present invention is to provide a method for obtaining clear dye images using a simple method.

That is, the present invention provides at least a photosensitive silver halide, a binder, a reducing agent for the photosensitive silver halide,
In addition, by heating a photosensitive material having a dye-donating substance that releases a mobile dye by combining with an oxidized form of a reducing agent to release a mobile dye, t! &nAt least one movable dye produced in an imagewise manner by the action of light and heating.
The seeds are transferred under high temperature conditions in the presence of a hydrophilic thermal solvent,
This is a dry image forming method characterized by forming a dye image by fixing the dye on a dye fixing layer.

In the photosensitive material according to the present invention, the exposed photosensitive silver halide is converted into a photosensitive silver halide by using the exposed photosensitive silver halide as a catalyst by heating in a substantially water-free state after or simultaneously with the imagewise exposure. Because a redox reaction occurs with the reducing agent, in addition to the silver image, the oxidized reducing agent undergoes a coupling reaction with the dye-donating substance, resulting in a mobile hydrophilic image. Since the dye is released, a dye image is also obtained at the same time. In the present invention, this developing step is
However, if this heat development is performed, unreacted dye-providing substances coexist and cannot be distinguished from the released mobile hydrophilic dye image. However, in the present invention, the dye of the dye image obtained at this time is
Since it is a mobile dye, we decided to move it to the dye fixing layer.

Therefore, a dye image with excellent image quality and storage stability can be obtained. This step is the "dye fixation" step in the present invention.

In the present invention, by making a hydrophilic thermal solvent exist, there is no need to supply a solvent for dye transfer from the outside, and therefore there is no need to supply any solvent at all in the entire process from exposure to development and fixation. Through processing, a dye image with good color reproducibility can be formed. Therefore, the photosensitive material used in the present invention does not need to be supplied with anything when the mobile dye is transferred, but even if a dye transfer solvent such as water is supplied, the effects of the present invention will not be hindered in any way. .

The principle of the present invention described by Mil is essentially the same whether a negative-tone emulsion or an autopositive emulsion is used as the emulsion of the light-sensitive material. Among the silver image and mobile dye image obtained in the exposed area, only the dye image is moved to the fixed dye J-, except that the dye WI with good color reproducibility is used in the same manner as when using a negative emulsion. You can get the image.

In the present invention, the redox reaction between the photosensitive silver halide and/or organic silver salt oxidizing agent and the reducing agent, and the subsequent cambling reaction between the reducing agent, which has become an oxidized product, and the dye-donating substance are substantially This can be caused by heating in a water-free state, but here, heating for dye image formation means heating at 80°C to 250°C, and in a substantially water-free state. This means that the reaction system is in equilibrium with the moisture in the air, and water is not specifically supplied to cause or promote the reaction. This situation is called “The th
theory of the ph.

tographic process″4thEd,
(Edited by T.H.James,
Macmillan), page 374.

In the present invention, the dye to be released can be selected by selecting the dye-donating substance, so that various colors can be reproduced. Therefore, by selecting a combination, it is possible to create a colored image, so the dye image in the present invention includes not only a monochrome image but also a multicolor image, and a monochrome image also includes a monochrome image obtained by mixing two or more colors. .

Conventional dye release reactions are thought to be caused by attack by so-called nucleophiles and are usually carried out in aqueous solutions with a high pH of 10 or more. It is extremely unusual that a high reaction rate can be achieved only by heating in a state substantially free of water (Japanese Patent Application No. 177,611/1982).

The above reaction proceeds particularly well when an organic silver salt oxidizing agent is present, and high image density can be obtained.

Therefore, it is a particularly preferred embodiment to coexist an in-house silver salt oxidizing agent.

The dye-donating substance that releases the hydrophilic mobile dye used in the present invention is represented by the general formula C-LD.

Here, C represents a substrate that binds to the oxidized product of the reducing agent produced by the reaction between the reducing agent and silver halide, and D represents the image-forming dye portion.

L represents a linking group between C and D, and the C-L bond is cleaved by the reaction between the oxidized product of the reducing agent and C.

The substrate C that can bind to the oxidized product of the reducing agent produced by the reaction between the reducing agent and silver halide is active methylene, active methine, phenol, naphthol residue, etc., and preferred substrates are those represented by the following general formula (1 ) to (■).

The following margins R1, R2, R3, R4 are shading, hydrogen atoms, argyl groups, cycloalkyl groups, aryl groups, alkoxy groups,
Aryloxy group, aralkyl group, acyl group, acylamino group, alkoxyalkyl group, aryloxyargyl group, N-substituted alkamoyl group, alkylamino group, ``I-arylamino group, halogen atom, acyloxy group, ``mesyloxydialkyl group'' These substituents further represent water groups, cyano groups, nitro groups, N-substituted sulfamoyl groups, carbamoyl groups, N-substituted rubamoyl groups, acylamino groups, group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, or an acyl group.

Substrate C has the function of bonding with the oxidized form of the reducing agent and releasing the °C-mobile dye, and also has a ballast group to prevent the dye-donating substance itself from diffusing into the dye-receiving image-receiving layer. There must be.

The ballast 1-group is preferably a hydrophobic group such as an alkyl group, an alkoxyalkyl group, or an aryloxyalkyl group, and these ballast groups preferably have a total carbon number of 6 or more, and the total carbon number of the substrate C is It is preferable that it is 12 or more. Preferred examples of substrate C are shown below, but are not limited thereto.

Margin below (C-4) th (C-14) rl　ρ (C-15) (C-16) (C-17) 1 The linking group connects the substrate C and the dye moiety. It was discovered that 2 1 dli 3'J Jl&.

n-0 to 3, n=l to 2 11=0 to 3, n=l to 3 n=(1 to 3, n-1 to 3-28
7-tt u2 Here, R, R' represent a hydrogen atom, a methyl group, or an ethyl group, and the benzene ring further represents a hydroxyl group, a sulfamoyl group, a methyl group, an ethyl group, an alkoxy group, a hydroxyalkyl group, It may be substituted with a hydroxyalkoxy group, an alkoxyalkoxy group, or a halogen atom.

Among these linking groups, those having a total carbon number of 12 or less and having high hydrophilicity are preferred because they give good results. Representative examples of these preferred linking groups are shown below.

-0--CH2CH2-(L-1) --0-CH2CH2CH2-(L-2)-O-CH2
CH2H-(L-3) -O-CH2CH2CH2CH2H-(L-4) H3 -o-tongue H-(L-5) -O-CI2CH20-(L-8) -DC)12CI2NHCO-(L-12) −〇Cf(
2Ctlz(]12Nt(Co-(1,-13)(L-
23) -NH3O2NHCONH- (L-24) Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, indigoid dyes, carbonium ion dyes, styryl dyes, di-I-mouth dyes, There are quinoline dyes 1, phthalocyanine dyes, etc., and representative examples of these are illustrated by hue next.

Yellow 1 12 Magenta If fi I2 Bar1/1n RI2 In the above formula, R11-Rlf5 is 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, Cyano group, hydroxyl group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group 1, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group,
Aryloxyalkyl group, nitro group, halogen, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-substituted carbamoyl group, sulfamide group, N-
, a substituted sulfamide group, a hydroxyalkoxy group, an alkoxyalkoxy group, a carboxyl group, an amino group, a 'substituted amino group, an alkylthio group, an arylthio group, a hydroxamic acid group, and an imide group.

As an image-forming dye, the following conditions must be met.

1) Hydrophilic 2. It has excellent mobility in a hydrophilic atmosphere, efficiently diffuses into the dye fixing layer, and dyes the dye fixing material at high concentration.

2) Must have a favorable hue in terms of color reproduction.

3) High molecular extinction coefficient.

4) Stable against light, heat, reducing agents, and other additives in the system.

5) It is easy to synthesize and can be incorporated into substrate C.

Examples of the group imparting m-aqueous property include a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, an imide group, a hydroxamic acid group, a quaternary ammonium group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, and a sulfamoyl group. Famoylamino group, substituted sulfamoylamino group, ureido group, substituted ureide group, alkoxy group,
Examples include hydroxyalkoxy group, alkoxyalkoxy group, and the like.

In the present invention, those whose hydrophilicity is significantly increased by proton dissociation under basic conditions are particularly preferred.
(pKa<12), including phenolic hydroxyl group,
Included are carboxyl groups, sulfo groups, sulfonic acid groups, imido groups, hydroxamic acid groups, substituted and unsubstituted sulfamoyl groups, sulfamoylamino groups, and the like.

Examples of preferred image-forming dyes that meet these requirements are shown below.

Yellow: (D-1))υINN';1 Image-forming dyes are not limited to those mentioned above, and may also be used as dye-donating substance precursors (leuco bodies, temporary short-wave conversion, etc.). good.

A dye-donating substance that releases a mobile dye does not itself diffuse into the dye-fixing layer, and only the dye released by reaction with the oxidized reducing agent stains the dye-fixing layer at a high concentration. desirable. Therefore, it is desirable that the dye-donating substance has a ballast group in the substrate C to prevent diffusion to the dye fixing layer, and does not have a group in the dye part that inhibits diffusion to the dye fixing layer. . Preferred specific examples of the dye-donating substance are shown below. .

Next, a method for synthesizing the dye-donating substance will be described.

The dye-donating substance of the present invention is General formula B / \ It is represented by LD.

Here, C: Substrate that binds to the oxidized product of the reducing agent B: Balladed group L: Connecting group of C and D Two image-forming dye moieties.

The dye-donating substance of the above general formula can generally be synthesized according to the following two schemes.

Scheme 1゜Scheme 2゜＼ -D Here, which method is used depends on the type of substrate C. For example, for particularly important substrates phenol and naphthol, the former is used in Scheme 2゜, and the latter is Scheme 1. is synthesized by In addition, the method for introducing baras I/group B differs depending on the type of substrate C. For example, in the case of a phenol type, it is introduced by acylation of the amino group at the 2-position, and in the case of a naphthol type, it is introduced by amidation of the carboxyl (or ester) group at the 2-position. Most common. On the other hand, introduction of the dye moiety is carried out using Scheme 1. In Scheme 2, the condensation reaction of both end groups of the connecting group and the dye moiety is generally carried out by the ab-cambling method. A specific synthesis example is shown below.

1. Synthesis of dye-donating substance (1) 1-a) 2-(N-hexadecylcarbamoyl)-
4-(2-(p-aminophenyl)ethoxy]~1-naphthol(1-a) 1,4-dihydroxy-2-naphthoic acid phenyl 56 g
(0.2 mol) was heated and dissolved in dimethylformamide of IQOmf, then 48.2 g (0.2 mol)
of hexadecylamine was added in small portions at 20°C to 30°C. After addition, heat at 70°C to 80°C for 3 hours, and heat at 30°C.
0 ml of methanol was added and the mixture was allowed to cool. The precipitated crystals were collected by filtration and washed with methanol. Yield was 71g.

Chemical formula % Formula % (01 19 g of phosphoric acid and 609 mA of toluene were mixed and heated under reflux for 5 hours, and the produced water was azeotropically distilled off.

After cooling, toluene was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate. After washing with water, ethyl acetate was concentrated under reduced pressure, and the residue was purified by silica gel chromatography to obtain 2-(N-hexadecylcarbamoyl)-4-(2-(p-nitrophenyl)ethoxy]-1-naphthol, 28 .2g of this crystal was obtained.17°3g (0.03mol) of this crystal, 2g of ammonium chloride, 200m of isopropanol!! and 2g of water.
The 0mj+ mixture was heated to 50°C. Next, reduced iron 1
2 g was added little by little at 50°C to 60°C, and after the addition, the mixture was heated under reflux for 1 hour. After hot filtration, the filtrate was allowed to cool and the precipitated crystals were removed and washed with methanol to give 2-(N-hexadecylcarbamoyl)-4-(2-(p-aminophenyl)ethoxy]-1- 14.1 g of naphthol (1-a) was obtained.

The following margin chemical formula 1-b) Dye-donating substance (1) 5.46 g (0.01 mol) of (1-a) was heated and melted in 5 Qml of methyl cellosolve, 3 ml of hydrochloric acid was added, and the mixture was cooled to 10°C. 0.7g of sodium nitrite in 2 parts of water
mA and added into the solution at 10°C to 12°C. After stirring for 20 minutes at 10°C, a small amount of sulfamic acid was added to destroy excess nitrous acid.

4-carboxyme-1-naphthol 2°18g (
0.01 mol) was dissolved in 20 ml of methyl cellosolve, 40 mJ of 10% potassium hydroxide methanol solution was added thereto, and then the above diazo solution was added at 5°C to 8°C. After stirring at 5° C. for 30 minutes, the mixture was neutralized with dilute hydrochloric acid, and the resulting reddish-purple precipitate was collected by filtration and recrystallized from ethyl acetate to obtain dye-donating substance (1).

2. Synthesis of dye-donating substance (2) (1-a) 5.46 g (0,
01 mol) was diazotized.

■-Lupoxymethyl-3-cyano-6-hydroxy-
4-methyl-2-pyridone, 2.08 g (0.01 mol), sodium hydroxide 0.4 g, sodium #acid 5 g,
The above diazo solution was added to a mixture of 30 ml of methyl cellosolve and 5 ml of water at 5°C to IO°C. 30 at 10℃
After stirring for a minute, acidify with dilute hydrochloric acid and collect the yellow crystals by filtration.
Dye-donating substance recrystallized from ahitonitrile (2) 5
．． 6g was obtained.

3. Synthesis of dye-donor i (3) 2-(N-hexadecylcarbamoyl)-4-(2-(p-nitrophenoxy)ethoxy]-1-naphthol was prepared in the same manner as in (1-3). Obtained.

17.8g (0.03 mol) of this stuff, 2g of ammonium chloride, 200mj of isopropanol! and water 20
The mixture of m j+ was heated to 50°C, then 12 g of reduced iron was added little by little at 50 to 60°C, and the mixture was heated under reflux for 1 hour.

After hot filtration, the filtrate was allowed to cool and the precipitated crystals were collected by filtration and washed with water and methanol to give 2-(N-hexadecylcarbamoyl)-4-(2-(p-aminophenoxy)ethoxy)-1- 15.ag of naphthol (3-a) was obtained.

(3-a) 5.62g (0.01mol) in 20mj of dimethylacetamide! , 10ml of tetrahydrofuran
and 5ml of pyridine! Melt it, then ice it? FF4-(
4-chlorosulfonylphenylazo)-2-N,N-diethylsulfamoyl-5-methylsulfonylamino-
5.75 g (0.01 mol) of 1-naphthol were added little by little.

After stirring at room temperature for 30 minutes, the reaction solution was poured into cold dilute hydrochloric acid.
The formed orange-red precipitate was collected by filtration. A purified product of dye-donating substance (3) was obtained by recrystallization from ethyl acetate.

4. Synthesis of dye-donating substance (4) (3-a>5.62 g (0.01 mol) was added to 20 ml of dimethylacetamide and 10 ml of tetrahydrofuran.
mj! and pyridine 5 m It, then 5
-(3-chlorosulfonylphenylsulfonylamino)
6.26 g (0.01 mol) of -4-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthol was added little by little under water cooling.

After the addition, the mixture was stirred at room temperature for 20 minutes, and the reaction solution was poured into cold dilute hydrochloric acid. The produced reddish brown precipitate was collected by filtration and purified by silica gel chromatography (methanol-chloroform) to obtain a dye-providing substance (4).

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2.322.0.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 27. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters ( TA solvents with high boiling points such as octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc.
or an organic solvent with a boiling point of 30°C to 160°C, such as ethyl acetate, lower fulkylacetate such as butyl acid, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone etc., and then dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Special Publication No. 51-39853, Japanese Patent Publication No. 51-59943
The dispersion method using polymers described in No.

In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g per 1 g of the dye-donating substance used.
It is as follows.

Examples of the silver halide used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, it is preferable to use silver halide containing silver iodide crystals in some of its grains.

Such silver halide exhibits a pattern of pure silver iodide as its X-ray diffraction pattern.

Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary halide emulsions, silver halide grains form perfect crystals. For example, when measuring X-ray diffraction of a silver iodobromide emulsion, no pattern of silver iodide crystals or silver bromide crystals appears, but an X-ray diffraction pattern appears at positions corresponding to the mixing ratio.

In the present invention, particularly preferred silver halides are silver chloroiodide, silver iodobromide, and silver chloroiodobromide, which contain silver iodide crystals in their grains and therefore exhibit an X-ray pattern of silver iodide crystals. .

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 halides have different sizes and/or halogen compositions! The above may be used in combination.

The average grain size of the silver halide used in the present invention is preferably from 0.0011 Im to IO#m, more preferably from 0.001 μm to 5 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, etc., compounds such as gold, platinum, palladium, rhodium and iridium, and halogenated silver halide. Chemical sensitization may also be achieved by the use of reducing agents such as tin or combinations thereof. For more information,
”The Theory of the Phot
o-g-raphlc Process” 4th edition, T.

H. James, Chapter 5, pages 149-169.

A particularly preferred embodiment of the present invention is one in which an organic silver salt oxidizing agent is used in combination, but the silver halide used in this case has the characteristic that it contains pure silver iodide crystals when silver halide is used alone. All silver halides known in the art can be used.

The organic silver salt oxidizing agent used in the present invention is produced at a temperature of 80° C. or higher, preferably at 100° C. in the presence of photosensitive silver halide.
When heated above C, reacts with the image forming substance or a reducing agent coexisting with the image forming substance as necessary,
It forms a silver image.

By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density.

Examples of such organic silver salt oxidizing agents include silver salts of organic compounds having a carboxyl group, including silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. There is salt etc.

Examples of aliphatic carboxylic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, silver salts of lauric acid,
salts, silver salts of capric acid, silver salts of myristic acid, silver salts of palmitic acid, silver salts of maleic acid, silver salts of fumaric acid, silver salts of tartaric acid, silver salts of furoic acid, silver salts of linoleic acid, oleic acid. Silver salts of acids, silver salts of adipic acid, silver salts of sebacic acid,
There are silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, silver salts of camphoric acid, etc. Also, silver salts substituted with halogen atoms or hydroxyl groups are also effective.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3゜5-dihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, and silver salts of m-methylbenzoic acid. , silver salt of p-methylbenzoic acid, 2,
Silver salts of substituted benzoic acids such as silver salts of 4-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, silver salts of phthalic acid. , silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid, US Patent No. 3.
3-carboxymethyl- described in No. 785,830
Examples include silver salts such as 4-methyl-4-thiazoline-2-dione, and silver salts of aliphatic carboxylic acids having a thioether group as described in U.S. Pat. No. 3,330.663.

In addition, there are silver salts of compounds having a mercapto group or a thione group and derivatives thereof.

For example, 3-mercapto-4-phenyl-1゜2.4-
) silver salt of lyazole, silver salt of 2-mercaptohenshiimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2-mercaptobenzthiazole, 2-
Silver salt of (s-ethylglycolamide)benzthiazole, 3-alkyl (alkyl group having 12 to 22 carbon atoms)
The w! of thioglycolic acid described in JP-A No. 48-28221, such as thioglycolic acetic acid! salts, silver salts of dithiocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamides, 5
-Silver salt of carboxy-1-methyl-2-phenyl-4-thiopyridine Silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt of mercaptooxadiazole, US Pat. No. 4,123.274 m
Silver salts described in the literature, such as I, 2,4-mercaptotriazole derivative 3-amino-5-pendylthio 1,2
゜Silver salt of 4-1-lyazole, U.S. Patent No. 3.3016
3-(2-carboxyethyl)-4 described in specification No. 78
-A silver salt of a thione compound such as a silver salt of methyl-4-thiazoline-2-thione.

In addition, there are silver salts of compounds having imino groups. For example, silver salts of benzotriazole and its derivatives described in Japanese Patent Publications No. 44-30270 and No. 45-18416, silver salts of alkyl-substituted benzotriazoles such as benzotriazole silver salts, methylbenzotriazole silver salts, 5- Chlorobenzo! ~Silver salt of halogen-substituted benzotriazole such as silver salt of riazole, 8N of carboimide benzotriazole such as silver salt of butylcarboimidobenzotriazole! Salt, U.S. Patent No. 4,220.7
1.2 described in the specification of No. 09. '4-triazole and 1-
Examples include silver salts of H-tetrazole, silver salts of carbazole, 816 of saccharin, and silver salts of imidazole and imidazole derivatives.

In addition, in the present invention, Research Disclosure V
o ], 170. Organic gold ri such as silver salts and copper stearate described in No. m17029 of June 1978
RPA can also be used in the same way as the various silver salts mentioned above. Two or more types of organic silver salt oxidizing agents can be used in combination.

The reducing agent used in the present invention has the ability to be oxidized by a silver halide and/or organic silver salt oxidizing agent, and its oxidized product reacts with a dye-donating substance to release an image dye. A color developer that forms an image by oxidative coupling is useful as a reducing agent having such ability.

As a reducing agent used in heat-developable color photosensitive materials, N,N-diethyl-3 is described in US Pat. No. 3,531,286.
-Methyl-p-ph, η-nylene diamine di(e i) p-phenylene color developers have been described.
No. 70 describes 7-minophenol. Particularly useful aminophenol reducing agents include: 4-7 minnow 2,6-cyclophenol, 4-7 minnow 2,6-
Examples include dibromophenol, 4-amino-2-methylphenol sulfate-14-amino-3-methylphenol sulfate, and 4-amino-2,6-cyclophenol hydrochloride. Furthermore, Research Disclosure Magazine No. 151 N09151 (+8,
U.S. Pat. No. 4,021,240 discloses 2,6-dichloro-4-HIS sruntonyl midophenol, 2,6-dichloro-4-HIS
-dipromo 4-substituted sulfonamidophenols and the like are described and useful. In addition to the phenolic reducing agents described above, naphthol reducing agents such as 4-amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful. Furthermore, as common color developing agents that can be applied, 7-minohydroxyvirazol derivatives are described in U.S. Pat. No. 2,895,825, and U.S. Pat.
The aminopyrazoline derivatives described in No. 2.714 are also published in Research Disclosure Magazine June 1980 No. 227-
230.236-240 pages (R1)-19412, RD
-19415) describes hydrazone derivatives and -C
There is. Even if these reducing agents are used alone, there are two types! ! 1
The above may be used in combination.

The reducing agent can be used in a certain concentration range. Generally useful reducing agent concentration ranges are about 0.000.0.0.0.0.0.0% reducing agent per mole of oxidized. From 1 mole to about 20 moles of reducing agent, particularly for use in the present invention, generally from about 0.1 mole to about 4 moles of reducing agent per mole of oxidizing agent.

In addition to the above-mentioned reducing agents, the following reducing agents can also be used as auxiliary developers.

Useful auxiliary developers include hydroquinone, tertiary
Alkyl substituted hydroquinones such as butylhydroquinone and 2,5-dimethylhydroquinone; catechols; pyrogallols; There are polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate,
Accorbic acid, A, Scorbin MH conductor R1N, N'
- Hydroxylamines such as di(2-ethoxyethyl)hydroxylamine, pyrazolidones such as l-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-birapritone, reductones, hydroxytetron Acids are useful.

Auxiliary developers can be used in a range of concentrations. Useful concentration ranges are o, oo for silver.

Particularly useful concentration ranges are 5 times molar to 20 times molar.
It is 0.001 times mole to 4 times mole.

Although the thermal development process during heating of the present invention is not fully clarified, it can be considered as follows.

When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. For this, '[', l(, J
“The Theory of T” by ame s
he PhotographicProcess”3
rd Edition, pages 105 to 14B.

Further, by heating the photosensitive material, the reducing agent of the present invention reduces the silver halide and/or the organic silver salt oxidizing agent using the latent image nucleus as a catalyst to produce silver, and the reducing agent itself is oxidized. The oxidized reducing agent and the dye-donating substance undergo an oxidative coupling reaction to release a hydrophilic dye. This reaction can be accelerated by nucleophiles. When an organic silver salt oxidizing agent is used in combination with an organic silver salt, it is necessary that the silver halide and the organic silver salt oxidizing agent be present at a substantially effective distance in order to quickly initiate the reaction. It is desirable that the silver oxide and the organic silver salt oxidizing agent exist in the same layer.

Development by heating differs from so-called wet development in that the reaction requires time because the diffusion of reactive molecular species is restricted. However, if heating for development takes too long, the thermal reaction in the unexposed area cannot be ignored and so-called capri occurs, which is undesirable.

In the present invention, a hot solvent can be used as one means for improving such disadvantages. The term "thermal solvent" herein refers to a non-hydrolyzable solvent that is a solid at ambient temperature but exhibits a mixed melting point with other components at or below the heat treatment temperature used. It refers to an organic material, and when it is heated and developed in the presence of a hot solvent, the development speed can be increased and the image quality can be improved. As such a thermal solvent used in the present invention, a compound that can serve as a solvent for a developer, a compound that is a substance with a high dielectric constant and is known to accelerate the physical development of a silver salt, and the like are useful. Useful thermal solvents include polyglycols described in U.S. Pat. No. 3,347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleic acid ester, beeswax, monostearin, -5o2-
Compounds with high dielectric constants having 1-CO- groups, such as acetamide, succinimide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, polar substances described in U.S. Pat. No. 3,667,959, and 4-hydroxybutanoic acid. Lactone, Methylsulfinylmethane, Tetrahydrothiophene-1,1-dioxide, Research Disclosure Magazine, December 1976 issue 26
1 on pages 28 to 28. lO-decanediol, methyl anisate, biphenyl perate, etc. are preferably used.

Although the role of the solubilizer in the present invention is not necessarily clear, it is understood that its main role is to promote the diffusion of reactive molecular species during development.

The photosensitive silver halide, organic silver salt oxidizing agent 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 used alone or in combination. This binder has
Hydrophilic materials can be used. Typical hydrophilic binders are transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, and natural substances such as polysaccharides such as starch, gum arabic, pullulan, and dextrin. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinylalco-Q/, polyvinylpyrrolidone, and acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. For these pigments, any peach that is commonly used as a basic heterocyclic nucleus for cyanine pigments can be applied. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pillow I nucleus, oxazole nucleus, thiazole nucleus,
Shibinazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei;
That is, indolenine nuclei, kari/zindolenine nuclei, indole nuclei, benzoxadole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include nuclei having a ketomethylene structure, such as birazolino 5-one nucleus, thiohydantoin nucleus, and 2-thioxazolidine-2.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl scattering, and the like can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.
No. 080, U.S. Patent No. 2,231,658, U.S. Patent No. 2,
No. 493.748, No. 2,503.776, No. 2
, 519,001, 2.912.329, 3.656,959, 3.672.897, 3,694°217, 4.025.349 ,
No. 4°046.572, British Patent No. 1. 242.
No. 588, Special Publication No. 44-14030, No. 52-2
Examples include those described in No. 4844.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

A typical example is a US patent! No. 82.688,545, No. 2,977.229, No. 3. 397. No. 060, No. 3.522.052, No. 3.527.641
No. 3,617.293, No. 3,628,96
No. 4, No. 3,666.480, No. 3,672.8
No.98, same%j3.679.428, same%j3.703
．． No. 377, No. 3.769, 301, No. 3.81
4.609, 3,837.862, 4.0
26゜707, British Patent No. 1,344,281, British Patent No. 1,507,803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Publication No. 110618-1987, Japanese Patent Publication No. 52-109925 It is mentioned in Salete.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with a nitrogen-containing heterocyclic group (e.g., U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehy 1
'condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc., U.S. Pat.
．． Particularly useful are the combinations described in No. 615.641, No. 3,617.295, and No. 3.635.721.

In the present invention, various dye release aids are used in various ways,
For example, it can be used by being included in any layer of a photosensitive material or any layer of a dye fixing material. A dye release aid is a photosensitive silver halide and/or
Or an organic silver salt that can promote the redox reaction between the oxidizing agent and the reducing agent, or can promote the dye release reaction that combines with the oxidized form of the reducing agent to release a mobile dye, and is a base or A base precursor is used. In the present invention, it is particularly advantageous to use these dye-releasing aids in order to accelerate the reaction, but when these dye-releasing aids are incorporated into the light-sensitive material, they do not impair the storage stability of the light-sensitive material. You have to choose something in particular.

Examples of preferable bases that can be used in photosensitive materials include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N
Mention may be made of -alkyl-substituted aromatic amines, N-hydroxyalkyl-substituted aromatic amines, and bis[p-(dialkylamino)phenylcomethanes. U.S. Pat. No. 2,410,644 discloses that betaine, tetramethylammonium iodide, and diaminobutane dihydrochloride are used in U.S. Pat. Compounds have been described and are useful.

The base precursor releases a basic component when heated. An example of a typical base precursor is British Patent No. 998,9.
It is described in No. 49. Preferred base precursors 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. U.S. Patent No. 3,220,8
Guanidine trichloroacetic acid described in No. 46 is particularly useful. Aldonamides described in JP-A No. 50-22625 are preferably used because they decompose at high temperatures to produce bases.

These dye release aids can be used in a wide variety of ways. A useful range is 50% by weight or less, preferably 0.01% to 4% by weight of the coated bellows of the photosensitive material.
It is in the range of 0% by weight.

In the heat-developable light-sensitive material of the present invention, it is particularly advantageous to use a compound represented by the following general formula because development is accelerated and dye release is also promoted.

[General formula]

In the above formula, At, A2, A3, and A4 may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue. represents a substituent selected from the following, and Al and A2 or A3 and A4 may be linked to form a ring.

Specific examples include H2N502NH2, H2N502N
(CH3)2, H2N502N (C2H5)2, H
2N5O2NHCH3, H2N502N (C2H40
H)2, CH3NH302NHCH3, etc.

The above compounds can be used in a wide range of applications.

A useful range is 20% by weight or less, more preferably 0.1 to 15% by weight, based on the weight of the coated bellows of the photosensitive material.

In the present invention, it is advantageous to use a water-releasing compound because it accelerates the dye-releasing reaction.

A water-releasing compound is a compound that decomposes during thermal development and releases water.
It refers to a compound that These compounds are particularly known in the transfer printing of fibers, and NH4F e (SO4)2.12H20 described in JP-A-50-811386 is useful.

The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and related materials. This includes films or resin materials. U.S. Patent No. 3,634
．． The polyesters described in No. 089 and No. 3,725.070 are preferably used. Particularly preferably, polyethylene terephthalate film is used.

The coating solution used in the present invention can be prepared by mixing separately formed silver halide and organometallic salt oxidizing agent before use, but it is also possible to prepare the coating solution by mixing the two separately. Mixing in a ball mill for hours is also effective. Another effective method is to add a halogen-containing compound to the prepared organic silver salt oxidizing agent and form halogen silver with the silver in the silver salt oxidizing agent.

For information on how to make these silver halides and organometallic salt oxidizing agents, how to mix them, etc., see Research Disclosure No. 17029, JP-A-50-32928, JP-A-51-42529, U.S. Patent No. 3, No. 700,458, JP-A-49-13224, JP-A-50-17216, and the like.

In the present invention, the coating amount of the photosensitive silver halide and organic silver salt oxidizing agent is 50 mg to 10 g in total in terms of silver.
m2 is appropriate.

The photographic emulsion M or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion,
Various surfactants may be included for various purposes such as preventing adhesion and improving photographic properties (eg, development acceleration, g! toning, sensitization).

For example, saponins (steroids), alkylene oxide derivatives such as polyethylene glycol, polyethylene oxide derivatives, etc. / glycol / polypropylene glycol condensate,
Polyethylene glycol furkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene [non-glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxynide adducts of silicone], glycidol derivatives (e.g. Nonionic surfactants such as alkenyl monosuccinic acid polyglypeptide, alkylphenol polyglyceride) fatty acid esters of polyhydric alcohols, and alumole esters of sugar;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl poly Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as oxyethylene alkylphenyl ethers and polyoxyethylene alkyl phosphate esters; Amino r! 11M,
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; complexes such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. ring quaternary ammonium salts,
and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles.

Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide.

Nonionic surfactants that meet the above conditions are widely used outside the field, and their structures, properties, and synthesis methods are well known. Representative known documents include 5u
rfactant Scioncc 5eriOs Volurnal
, Nonjonlc 5urfactants (1'
4di1. cd by Marl in -1゜5)tick, λIarc-;111nkkarInc
, 196? >, 5urfacQ Active Ethylene C1xldaA
dduc L s (Schour e td t,
N@Pergamon Pr,ess 1969)
etc., and nonionic surfactants described in these documents that do not meet the above conditions are preferably used in the present invention.

These non-1"-ionic surfactants can be used alone or as a mixture of two or more.

The polyethylene glycol type nonionic surfactant is used in an amount of equal weight N or less, preferably 50% or less, based on the hydrophilic binder.

The photosensitive material of the present invention can contain a cationic compound having a pyridinium salt. An example of a cationic compound with a pyridinium group is PSA Journal.
al, 5ecLion B56 (1953), υ
SP2,648,604, USP3,671,247,
It is described in Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 44-9503, etc.

In the light-sensitive material used in the present invention, a compound that activates development and simultaneously stabilizes iii* can be used. Among them, 2 described in U.S. Patent No. 3,301゜678
- Hydroxyethylisothiuronium, isothiuroniums represented by trichloroacetate, U.S. Patent No. L
Bisisothiuroniums such as 1,8-(3,6-thioxaoctane)bis(isothiuronium trifluoroacetate) described in No. 669.670, West German Patent No. 2
thiol compound described in publication No. 162.714, 2-amino-2-thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiazolium trichloroacetate, etc. Thiazolium compounds, U.S. Patent No. 4,060,4
Bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) described in No. 20, 2-amino-2
-Compounds having α-sulfonylacetate as an acidic moiety, such as thiazolium phenylsulfonylacetate; compounds having 2-carboxycarboxamide as an acidic moiety, as described in U.S. Patent No. 4.088.496; is preferably used.

In the case of the present invention, since the dye-donating substance is colored, there is also an irradiation-preventing substance, a halogen-preventing substance,
Alternatively, although it is not so necessary to incorporate various dyes into the photosensitive material, in order to improve the sharpness of images,
Publication No. 48-3692, U.S. Patent @3.253,
No. 921, No. 2.527.583, No. 2,956
, No. 879, etc., such as filter dyes and absorbent substances, which are described in the respective Mei IIBIF, can be contained.

Further, these dyes are preferably ones that are capable of decolorizing rapidly, such as those described in U.S. Pat. Nos. 3.769,019 and 3.745.
, No. 009, No. 3. 615. Dyes such as those described in No. 432 are preferred.

The photosensitive material used in the present invention may contain additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, and an intermediate layer. ,A
It can have a H layer, a peeled NN, etc. For various additives, see Research Disclosure Magazine Vol.1.1
70. Additives described in No. 17029 of June 1978, such as plasticizers, sharpness-improving dyes, AH
Dyes, sensitizing dyes, capping agents, surfactants, fluorescent brighteners,
There are additives such as anti-fading agents.

In the present invention, as with the heat-developable photosensitive layer, the t! For the layer, intermediate layer, lower layer, bank layer and other layers, respective coating solutions are prepared and applied by dipping method, air knife method, curtain coating method or the method described in U.S. Pat. A photosensitive material can be produced by sequentially coating onto a support using various coating methods such as hopper coating and drying.

Further, if necessary, as described in U.S. Pat. No. 2,761.791 and British Patent No. 837.095,
It is also possible to apply 2N or more at the same time depending on the method.

In the present invention, the latent image obtained after exposure of the photosensitive material is maintained at a moderately elevated temperature, such as from about 0°C to about 250°C, for about 0.5 seconds to about 300 seconds. The image can be developed by heating the entire image. As long as the temperature is within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time.

A temperature range of about 10°C to about 160°C is particularly useful.

The heating means includes a simple hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc.
Or a method using a similar method can be used.

In the image forming method of the present invention, in which an image formed by a mobile hydrophilic dye is transferred to a dye fixing medium under high temperature conditions in the presence of a hydrophilic thermal solvent, the transfer of the mobile dye is initiated at the same time as the release of the dye. It may also be carried out after the release of the dye is completed. Therefore, heating for transfer may be performed after heat development or at the same time as heat development. Simultaneously with thermal development means that the heating for development also acts as the heating for the transfer of the released dye at the same time. Since the optimal temperature for development, the optimal temperature for dye migration, and the heating time required for each do not necessarily match, the temperatures can be set independently.

Heating for dye transfer is from 60°C to 250°C from the viewpoint of storage stability and workability of the photosensitive material, so in the present invention, it functions as a hydrophilic thermal solvent within this temperature range. You can choose one as appropriate. It goes without saying that hydrophilic thermal solvents must be able to quickly aid the movement of dyes when heated, but if we also consider the heat resistance of photosensitive materials, we need to consider the melting point required for hydrophilic thermal solvents. is 40°C to 250°C, preferably 40°C to 200°C, more preferably 40°C to 15Q-°C.

The "hydrophilic thermal solvent" in the present invention is a compound that is in a solid state at room temperature but becomes a liquid state when heated,
(Inorganic/Organic) Value>1 and solubility in water at room temperature is defined as a compound of 1 or more. Here, inorganic and organic are concepts for predicting the properties of compounds, and the details can be found in For example, in the field of chemistry, Volume 1719.
(1957).

Since the hydrophilic thermal solvent has the role of assisting the movement of the hydrophilic dye, it is considered preferable that it is a compound that can act as a solvent for the hydrophilic dye.

- In general, it is known from experience that the preferred solvent for dissolving organic compounds is that the (inorganic/organic) value of the solvent is close to the (inorganic/organic) value of the organic compound. . On the other hand, the (inorganic/organic) value of the dye-donating substances used in the present invention is around 1, and the value of the dye-donating substances is around 1, and the value of the dye-donating substance is about 1. The (organic) value is larger than the (inorganic/organic) value of the dye-donating substance, preferably 1.5 or more, particularly preferably 2 or more. It is preferable that the hydrophilic thermal solvent used in the process should move only the hydrophilic dye and not the dye-donating substance, so its (inorganic/organic) value is the value). That is, as a hydrophilic thermal solvent, it is essential that the (inorganic/organic) value is 1 or more.

conditions, preferably 2 or more.

On the other hand, from the viewpoint of molecular size, it is considered preferable that there be molecules around the moving dye that can move by themselves without inhibiting the movement. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 100 or less.

The hydrophilic thermal solvent of the present invention only needs to be able to substantially assist the movement of the hydrophilic dye generated by heat development to the dye fixing layer, so it can not only be included in the dye fixing layer, but also A hydrophilic heat solvent can be contained in a photosensitive material such as a photosensitive layer, or in both a dye fixing layer and a photosensitive layer, or in a photosensitive material or in an independent dye fixing material having a dye fixing layer. It is also possible to provide a separate layer containing . From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto.

Hydrophilic thermal solvents are usually dissolved in water and dispersed in the binder, but alcohols, such as 1. It can also be used by dissolving it in methanol, ethanol, etc.

The hydrophilic thermal solvent used in the present invention is 5 to 500% by weight, preferably 20 to 200!11%, particularly preferably 30 to 15% by weight of the total coating amount of the photosensitive material and/or dye fixing material.
It can be used in a coating amount of %N.

Examples of the hydrophilic heat solvent used in the present invention include ureas,
Pyridines, amides, sulfonamides, imides,
Mention may be made of alcohols, oximes, and other heterocycles.

Next, specific examples of the hydrophilic heat solvent used in the present invention will be shown.

Below margin n2NAN (C2H40H) 2 (11) (12) 309- (34) (35) CH3302NH2, HOCH2SO2NH2 (3G)
(37) HnIsu5o2h+H2,3HCNH3O2Nl2(3
B) (39) (40) (41) (43) (44) Product, (47) HOCH2 (CHOH) 3CH20H2 (4B)
(49) CH2O(CH)O
H) 3, C21(5C(CH20H) 3(50)
(51)02NC(CH2
0H) 3, Sorbit (52)
(53) (54) EIOCH-CH-CH-CH20H (55)
(56) CH3CH=NOH,HON-CICI-NOI((5
9) <60) (61) (62) Among these, ureas (1), (2), (3), (
10), pyridines (17), (19), amides (26), (30), (33), sulfonamides (34), (36), imides (40), (41) )
, (43), (44) and alcohols (46), (
54) is particularly preferred. Further, the hydrophilic heat solvent used in the present invention can be used alone or in combination of two or more.

In the present invention, the dye fixing layer moves the imagewise generated hydrophilic mobile dye under high temperature conditions in the presence of a hydrophilic thermal solvent, and fixes the dye image by receiving the mobile dye. is necessary. For this purpose, in the present invention, at least silver halide, its reducing agent, a dye-donating substance and a binder that combine with an oxidized form of the reducing agent to release a mobile dye, and, if necessary, an organic silver salt oxidized a photosensitive layer (1) containing an agent, and a dye fixing layer (If
).

The photosensitive layer (1) and the dye fixing layer (IF) may be formed on the same support, or may be formed on separate supports. The dye fixing layer (II) and the photosensitive layer (I) can also be separated. For example, after imagewise exposure, uniform thermal development can be carried out, and then the dye fixing layer (II) or the photosensitive layer can be peeled off.

In addition, when a photosensitive material in which the layer (1) is coated on the support and a fixing material in which the fixing layer (1) is coated on the support are formed separately, the photosensitive material Imagewise exposure゛ζ
After uniform heating, the fixing material is molded and the mobile pigment is transferred to the fixing layer (II
). In addition, photosensitive materials
, and then layered with a dye fixing layer (■).
There is also a method for uniform heating.

Light-sensitive material and color: 3'. Normal methods such as using a pressure roller can be used to bring the material into close contact with the fixing material, but in order to ensure sufficient contact, heating should also be used during the contact. You can also do it.

If the surface of the photosensitive material and the dye-receiving surface of the dye-fixing material are brought into close contact and heated after image exposure or after heat development at the same time as image exposure, the heating need only contribute to dye migration. Therefore, from this point of view, the heating temperature and heating time can be set independently of the heating for development.

When this method is adopted, it is preferable to complete the reaction for development in a short period of time so that the heating for development does not contribute to dye migration as much as possible; In order to obtain a clear image, it is necessary to keep the heating to transfer the dye to the dye transfer layer as low as possible within a reasonable transfer time so as not to cause a thermal reaction in the unexposed areas. preferred.

The dye fixing layer (n) may have a white reflective layer.

For example, a layer of titanium dioxide dispersed in gelatin can be provided on a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque Ia, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer. As the dye transfer aid, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used.

Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. The dye transfer aid may be used by moistening the image-receiving layer with a solvent, or may be incorporated into the material in the form of crystal water or microcapsules.

The dye fixing layer contains a dye mordant for fixing the dye, a hydrophilic heat solvent to aid the movement of the dye, a dye release reaction, etc.
A base and/or a base precursor for the reaction, and furthermore,
A binder may be included to bind these together. When the dye fixing layer is provided on a support L separate from the light-sensitive material, it is a particularly preferred embodiment to contain a base and/or a base precursor.

When the dye mordant is a polymer mordant, it also functions as a binder, so 1. In such cases, the amount of Ba Ingu may be reduced or the binder may not be used. On the other hand, Ba Ingu used it as a mordant7
Similarly, when the dye mordant has the same function as the dye mordant, it is also possible to omit the use of the dye mordant.

As the binder, the same kind of binder as used in photosensitive materials can be used.

The mordant used in the dye fixing layer of the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordant refers to a polymer containing secondary and tertiary amino groups,
Polymers having a nitrogen-containing heterocyclic moiety and polymers containing these quaternary cation groups, etc., with a molecular weight of 5,000 to 5,000.
200°,000, especially 10,000 to 50,000. For example, U.S. Pat. No. 2,548,564;
Vinylpyridine polymers disclosed in US Pat. No. 2,484,430, No. 3,148.061, US Pat. 3.625.694, 3,859,096, 4.12E1. Polymer mordants capable of cross-linking with gelatin, etc. disclosed in U.S. Pat. No. 3,958,995 and U.S. Pat. No. 2,721.85
No. 2, No. 2,798.063 4. Japanese Patent Publication No. 54-11
No. 5228, No. 54-145529, No. 54-126
Aqueous sol type mordant disclosed in No. 027 specification etc.;
U.S. Pat. No. 3,898,088”
water-insoluble mordant; U.S. Patent No. 4.1 (i8,976
A reactive mordant capable of forming a covalent bond with the dye disclosed in Specification 1 of JP-A No. 54-137333; furthermore, U.S. Pat.
No. 55, No. 3,642.4112, No. 3. ．． 18
8.70 (I, No. 3, 557, 06 G
No. 3.271, l 47 '3' = No. 3,
No. 271.148, Japanese Patent Publication No. 1983 7133'2, No. 5
No. 3-30328, 52 1 +) 5528';
+, No. 53-125, No. 53-I O21, and furthermore, rice (1 (¥ 2,6
No. 75.316, No. 2.882. The mordants described in the L56q specification may also be mentioned.

Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used.

Particularly preferred polymer mordants are shown below.

(1) 4! A group that has an ammonium group and can be covalently bonded to gelatin (for example, an aldehyde group, a chloroalkanoyl group, a chloroalkyl group, a vinylsulfonyl group,
Polymers having pyridinium propionyl groups, vinyl carbonyl groups, alkylsulfonoxy groups, etc., such as CH-CH-)--1÷CH2-CH1 (2) Repeated exposure of the seven-mer expressed by the following general formula reaction products of copolymers consisting of repeating units of other ethylenically unsaturated monomers and crosslinking agents (e.g. hahisalkanesulfonates, hisalenesulfonates).

aryl group, or b At least R3-R5 The two are joined together to form Peter. It may form a ring.

X: anion (the above alkyl groups and aryl groups include substituted ones) (4) (3) Polymer X represented by the following general formula: about 0.23
〜about j molar coefficient y: about θ to about 0 mol% Z: about 10 to about 0 mol% A: monomer having at least λ ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated monomer Q: N, P bb Ro, R2, R3: an alkyl group, a cyclic hydrocarbon group, or at least two of R to Rb3 may be combined to form a ring. (These groups and rings may be substituted.) Copolymer X consisting of (a), Φ) and (C): hydrogen atom, alkyl group or halogen atom (the alkyl group may be substituted) (b) Acrylic ester (C) Acrylic nitrile (5) Water-insoluble polymer having //3 or more repeating units represented by the following general formula bb R, R2, R3: each represents an alkyl group, R The total number of carbon atoms in engineering to R3 is /, 2 or more. (
Alkyl groups may be substituted. ) X: As the gelatin used for the anion mordant layer, various known gelatins can be used. For example, gelatin with different manufacturing methods such as lime-treated gelatin and acid-treated gelatin, or
It is also possible to use 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. You can, but
It is preferable to use a mordant/gelatin ratio of 20/10-40/20 (weight ratio), a mordant application amount of 0, and t-4Q/m2.

A typical dye-fixing material used in the present invention is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support.

When the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. As such a protective layer, one generally used as a protective layer for photosensitive materials can be used as is, but if the dye fixing layer is provided on the dye fixing material separately from the photosensitive material, In order not to inhibit the movement of the hydrophilic dye, it is preferable to impart hydrophilicity to the protective layer as well.

The photographic light-sensitive material and dye fixing material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimedylhydantoin, etc.), dioxane derivatives (2,3-dihydantoin, etc.) Roxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-,-tosahydro-!i-) riazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2, 4-dichloro-6-hydroxy-3-1 riazine, etc.), mucohalogen acids (Mukoclo Q4, Mufufe, Tukidichloroic acid, etc.), etc. can be used alone or in combination.

Further, as the heating + stage for moving the dye, various means similar to the heating means used in heat development as described above can be employed.

In the present invention, as well as the heat-developable photosensitive layer, a dye fixing layer,
Ho 11! [For the intermediate layer, undercoat layer, back layer, and other layers, prepare the coating solution for each layer.2. Dipping method, air knife method, curtain coating method or U.S. Pat. No. 3,681
A photosensitive material can be prepared by sequentially coating a support using various coating methods such as the hopper coating method described in , 294r+ and drying.

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.

In the present invention, various exposure means can be used. A latent image is created by image-like pure light of radiation including visible light.
C can be obtained. In general, light sources used for normal color printing, such as halogen lamps such as tungsten lamps, mercury lamps, and cord lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light emitting diodes, are used as light sources. You can use it.

As an original drawing,! Line i of diagram i! ! Of course, the Ii statue may be a photographic image with a floor space. It is also possible to photograph portraits of people and landscapes using a camera. j
Even if the "Yakii from the East" is printed in close contact with the original drawing,
Reflection printing may be performed, or enlargement printing may be performed.

In addition, the image information taken by a video camera, etc.]2 or sent from a television station is sent directly to a CRT or FOT, and this image is formed on a heat-developable photosensitive material, either closely or through a lens. , it is also possible to burn it.

Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively emits blue light, so in order to reproduce color images using LEDs, 3wi, which emits line light, red light, and infrared light, is used. The needles may be set so that the portions of the photosensitive material that are sensitive to these lights emit yellow, magenta, and cyan dyes, respectively.

That is, the green-sensitive portion (layer) may contain a yellow dye-providing substance, the red-sensitive portion (layer) may contain a magenta dye-providing substance, and the infrared-sensitive portion (layer) may contain a cyan dye-providing substance. . Other combinations are also possible as required.

In addition to the method described above, in which the original drawing is directly attached or projected, the original drawing illuminated by a light source is read by a light-receiving element such as a phototube or CCD, and this information is stored in the memory of a computer or other device as needed. After performing so-called image processing, this image information is reproduced on a CRT,
There is also a method of using this as an image-like light source, or of directly causing the three types of LEDs to emit light based on the processed information.

The image forming method of the present invention is an extremely simple image forming method that can perform completely dry processing in all steps from exposure to heat development and dye fixation without supplying any solvent from the outside. be. Furthermore, it is not only possible to maintain the sensitivity of conventional so-called silver halide photographic light-sensitive materials;
Since the formed dye image is fixed on a dye fixing material, the quality and storage stability of the dye image are extremely good, and the color reproducibility is good, and even though it is a completely dry process, color image reproduction is sufficient. This is extremely useful.

The image forming method of the present invention having such characteristics can meet not only the field of photography but also the recent demand for converting so-called soft images to hard images. is fixed in the pigment-fixed layer, so
Since the III image has good storage stability, it surpasses conventional photographic technology in that it can be easily used even when long-term storage is required, and the present invention is of great significance.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Margin Example 1 below. Preparation of silver iodobromide emulsion 40 g of gelatin,! :KBr26g, water 3000ml
The solution was stirred while maintaining the temperature at 50°C. Next, add 34g of silver nitrate to 200mj of water! A solution prepared by dissolving 3.3 g of potassium iodide in 100 ml of water was added to the above solution over a period of 2 minutes.

The pH of the silver iodobromide emulsion thus prepared was adjusted to 6.0 after removing the sediment and excess salt.
00 g of silver iodobromide emulsion was obtained.

Example 2. m gelatin 2 with benzotriazole silver emulsion
8g and 13.2g of benzotriazole in 3000mg of water
The garlic was dissolved and the mixture was stirred while keeping the skin at 40°C. A solution prepared by dissolving 17 g of silver nitrate in 100 mj2 of water was added to this solution over 2 minutes.

The pH of this Hengu-Riazole emulsion was adjusted to 6.0 after precipitation and removal of excess salt.
1. A yield of 400 g of benzotriazole silver milk was obtained.

Example 3 Preparation of hensitriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and 10 g of gelatin were added to 10 g of water.
00 mJ, and the solution was stirred while being maintained at 50°C. Next, a solution of 5 g of nitric acid #IB dissolved in 100 m6 of water was added to the above solution over a period of 2 minutes.

Next, add 1.2 g of potassium bromide to 50 mJ of water! The emulsion prepared by adding the solution dissolved in
1I to remove excess salt, the emulsion was
H was adjusted to 6.0. Yield was 200g.

Example 4 Preparation of gelatin dispersion of dye-donating substance 10 g of dye-donating substance (1), 0.5 g of sodium succinate 2-ethyl-hexyl ester sulfonate as a surfactant,
Weigh out 1 Og of trire resin phosphate (TCP), add 2 Og of cyclohexanone (Jrnl), and add about 60
The mixture was heated and melted at ℃ to form a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was stirred and mixed with a homogenizer for 10 minutes. Dispersed using OOOPPM.

Example 5. Preparation of photosensitive material E-1 (a) Silver iodobromide emulsion (Example 1) 2g (b) Benzotriazole emulsion (Example 2) g (C) 10% gelatin aqueous solution 2g (d) Dye-providing substance (1) ) gelatin dispersion (Example 4)
2.5g (6) 10 of guanidine trichloroacetic acid
% ethanol l volume? & 0.5m1(f)
2.6-dichloro-4-aminophenol 10% methanol solution 0.5 mj (h) Water 4.5 mj! After mixing and heating the above (a) to (h),
It was applied onto a polyethylene terephthalate film having a thickness of 180 μm so that the wet film thickness was 85 μm.

Furthermore, on top of this, 1.5 g/gelatin J- is added as a protective layer.
m2@ installed photosensitive material E-1 made WL7'C.

Example 6. Preparation of Photosensitive Material E-2 The dye-donating substance (4) was prepared in the same manner as in Example 4, except that the dye-donating substance (4) was used instead of the dye-donating substance ffi (1) used in Example 4. ) gelatin dispersion
! iII! (1) Silver iodobromide emulsion (Example 1) 5.5g (j) 10%
Gelatin aqueous solution 2g (k) Gelatin dispersion of dye-donating substance (4) 2.5g (1) 10% ethanol solution of guanidine trichloroacetic acid 0. 5 mJ (m) 2. 10% methanol solution of 6-dichloro-4-aminephenol 0.
5m1 (n) 59-6 aqueous solution of the compound with the following structure 1mA (0)
6 ml of water The above (1) to (o) were mixed and dissolved by heating, and then applied onto a polyethylene terephthalate film having a thickness of I 80 /Z m to a wet film thickness of 85 μm. On top of the film thus formed, 1.5 g/m2 of gelatin was further coated as a protective layer.
2 was produced.

Example 7. Preparation of Photosensitive Material R-3 In Example 6, dye-providing compound (2) was used instead of dye-providing compound (4), and instead of silver iodobromide emulsion,
Benzotriazole silver 5 containing photosensitive silver bromide of Example 3
．． A photosensitive material 14E-3 was prepared in exactly the same manner as in Example 6 except that 5 g was used. Preparation of Photosensitive Materials E-4 to E-6 The procedures of Examples 5 to 7 were repeated except that 2,6-dichloror+-4-aminophenol was removed from the preparation of Photosensitive Materials E-1 to E-3 in Examples 5 to 7, respectively. Photosensitive material E was prepared in exactly the same manner as in 7.
-4 to 6 were produced.

Example 98 Preparation of dye-fixing material R-1 Poly(methyl acrylate-co-N,N,N-1-dimethyl-N-vinylbenzylammonium chloride)
(Ratio of methyl acrylate and vinylbenzylammonium chloride was i:1) 10 g was dissolved in 200 ml of water and uniformly mixed with 100 g of 10% lime-treated gelatin. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 90 μm.

On top of this, the following (p) to (i) were mixed and melted, and then a dihydrophilic hot solvent layer was uniformly applied to a wet film thickness of 60 μm and dried.

<p) Urea 4" (q) Ice IQrn/ (r) Polyvinyl alcohol: 1-l (degree of saponification 98%) i
o point weight 9 stone aqueous solution 12 g Compound of (S')'-F structure 1 o 0 mg% aqueous solution 0.5 ml Example 10 Preparation of dye fixing materials R-2 to 40 Instead of 4 g of urea used in Example 9 Dye fixing material R-2 was prepared in exactly the same manner as in Example 9 except that 4 g of pyridine N-oquinide was used.

Similarly, dye fixing materials R-3 and R-4 were prepared using 4 g of sulfonamide and 4 g of acetamide, respectively.

Example 11 Preparation of dye fixing materials R-5 and R-6 Instead of 4 g of urea used in Example 9, 2 g of urea and N
- Dye fixing material R-5 was prepared in the same manner as in Example 9, except that 2 g of methyl urea was mixed and used.

Similarly, urea 1g, N-methylurea 1g, ethylurea 1g
g, dye fixing material R- by mixing and using 1 g of ethylene urea
6 was produced.

Example 12 Preparation of dye fixing materials R-7 and R-8 Application of the hydrophilic thermal solvent layer used for producing dye fixing material R-1 of Example 9 and dye fixing material R-5 of Example 11 10 of 2,6-dichloro-4-aminophenol in the solution.
11 color dye fixing material R-
7 and R-8 were produced.

Example 13. Heat development and dye transfer side Photosensitive material E-1 was imagewise exposed for 10 seconds at 2000 lux using a tungsten light bulb. Thereafter, it was heated uniformly for 40 seconds on a heat block heated to 140°C.

Next, the dye fixing materials were placed in close contact with the coated surfaces of R-1 to R-6, and placed on a heat block at 120°C for 30 minutes.
Heated for 0 seconds.

When the dye-fixing material was peeled off from the photosensitive material sheet, a negative magenta color image was obtained on the dye-fixing material. Table 1 shows the results of measuring the density of this negative image using a Macbeth density needle ('F, D-504).

Margin table below - 1 Dye solid Hydrophilic thermal solvent Maximum minimum fixed material Concentration Concentration -
−'−'−−□ −−−− (Unexposed area) R-1 urine!
133 0.15R-2 Pyridine N-oxide 1.38 0.18R-3
x Sulfonamide 1.1[t O,1
2R-47 Seto 7 MiF 1.10
0.09R-5 Urine i/N-/f-urea 1.
29 0.14R-6 urea/N-methylurea/ethyl urine #,/ethylene urine t= 1.35 0.
17 From the above results, it was demonstrated that by using a dye fixing material containing a hydrophilic thermal solvent, a high maximum density LII image can be obtained without supplying any water at all.

In addition, a dye fixing material (R
-5,6), the surface has excellent gloss,
I was able to obtain particularly sharp images.

Example 14. Thermal Development and Dye Transfer Example The photosensitive materials E-1 to E-3 of Examples 5 to 7 were exposed to light and heat developed in the same manner as in Example 13.

These were placed in close contact with the dye fixing material R-1 of Example 9 with the coated surfaces facing each other, and placed on a heat block for 12 hours.
Heated at 0°C for 30 seconds. When the dye-fixing material was peeled off from the photosensitive material sheet, negative magenta, cyan, and yellow color images were obtained on the dye-fixing material, respectively. Is this a negative image? It was measured using a Kubes densitometer ('IT' D-504).The results are shown in Table 2.

Table-2 Photosensitivity Dye Donation Hue Maximum Minimum Color Substance Concentration Concentration E-1 (1)
Magenta 1.33 0.15E-2 (4)
Cyan 1.58 0.21B-:3 (2
) Yellow 1.10 0.13 Example 15
．． Photosensitive material E-4 of Example 8 on heating thermal development and dye transfer side
Image exposure was performed for 10 seconds at 2000 lux using a tungsten bulb. These light-sensitive materials were used as dye fixing materials R-7 and R-8 of Example 12, respectively.
1 on the heat block, facing the coated side.
It was heated at 30°C for 30 seconds.

When the dye fixing material was peeled off from the photosensitive material sheet, negative magenta, cyan, and yellow color images corresponding to each photosensitive material were obtained on the dye fixing material. What is the density of these negative color images? It was measured using a Kubes densitometer (TD-504). The results are shown in Table-3.

Below F margin table-3 Photosensitive material Dye fixation Maximum density Minimum density material E-4R-71,180,16 E-5R・7 1.20 0.18E-6R-・
7 1.00" 0.15B-4R-111,
12,11,20 B-5R-81,150,17 E-6R-81,010,13 From the above results, even when heat development and dye transfer are performed at the same time, a dye image with high weave density can be obtained. It is true that it is possible to be
Corrected.

Example 16゜Photosensitive material E-7 was prepared in the same manner as in Example 5 except that 1.5 g of hydrophilic heat solvent (1) urea was newly added to the coating solution for photosensitive material E-1 of Example 5. I made it 7 times.

Furthermore, in dye fixing material 14R-1 of Example 9, dye fixing material R-10 was produced in exactly the same manner as in Example 1 except that the amount of urea applied in the hydrophilic heat solvent layer was reduced to 1/2.

Photosensitive material E-7 was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb, and then uniformly heated at 130° C. for 20 seconds. Next, each coated surface was brought into close contact with dye fixing material R-10, facing each other, and heated at 120° C. for 20 seconds. When the dye-fixing material is peeled off from the light-sensitive material,
A high density negative magenta image was obtained on the dye fixing material. The density of this negative color image is measured using the Macbeth density needle (TD-5).
04), the maximum density was 1.37 and the minimum density was 0.22. It has been demonstrated that even by incorporating a hydrophilic thermal solvent into a photosensitive material, it is possible to obtain a high density dye image by heating for a short time without supplying any water at all.

Example 17 Dye fixing material R-9 used in the present invention was prepared as follows.

Poly(methyl acrylate-N,N,N-)dimethyl-N-vinylbenzylammonium chloride
Ride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1; l) and 25 g of hydrophilic heat solvent (1) in 200 m7! Dissolved in water, 10%
It was uniformly mixed with 100 g of lime-treated gelatin. Spread this mixture onto a 90μ polyethylene terephthalate film.
It was applied uniformly to a wet film thickness of m.

Poly 1''nyl alcohol was applied onto the film thus formed to a dry film thickness of 1.5 μm to prepare a dye fixing material R-9.

Photosensitive material E-1 was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated uniformly for 20 seconds on a Heat Pro 2 heated to 140°C.

Next, each coated surface was brought into close contact with dye fixing material R-9, facing each other, and heated at 120° C. for 30 seconds on a heat block.

When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta color image was obtained on the dye-fixing material.

The density of the negative image thus formed was measured using a Macbeth density needle (TD-504), and the maximum density was 1.
29, and the minimum concentration was 0.18.

Thus, it has been demonstrated that by using a dye-fixing material containing a hydrophilic thermal solvent in the dye-fixing layer, images with high maximum density can be obtained even without supplying any water.

'1 filed as agent for Tomigami Photo Film Co., Ltd.
Patent Attorney Taki 1) Kiyoshi Akira 311

Claims (1)

[Claims] A photosensitive material having, on a support, at least a photosensitive silver halide, a hydrophilic binder, a reducing agent for the photosensitive silver halide, and a dye-donating substance that releases a mobile dye by bonding with an oxidized form of the reducing agent. The movable dye is imagewise formed by heating after exposure or at the same time as image exposure, and is fixed to the dye fixing layer by moving it under a high temperature condition in the presence of at least one kind of hydrophilic thermal solvent. Dry type i! iI image formation method.