JPS59180548A - Image forming method - Google Patents

Abstract

PURPOSE:To form a dye image which is the negative of a silver image by heating in a state in which water is not practically contained by using a photosensitive material contg. a reducing agent capable of reducing photosensitive silver halide at a high temp. and a specified diffusion resistant dye providing substance. CONSTITUTION:A photosensitive material contg. photosensitive silver halide, a binder, a reducing agent capable of reducing the photosensitive silver halide at a high temp., and a diffusion resistant dye providing substance which releases a movable dye on a support is imagewise exposed and heated in a state in which water is not pracitally contained to form imagewise the movable dye. The dye providing substance is represented by formula A (where each of R1 and R2 is a substituent, X is a bivalent combining group or a simple bond, and Y is S or Se, and Z is a group of atoms required to complete a 5-, 6- or 7-membered heterocyclic ring), and it causes a reaction for cleaning the heterocyclic ring contg. N and S or Se at a high temp. in the presence of silver ions or a soluble silver complex to release the movable dye.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a new method for forming dye images (negative relative to silver images) by heating in a substantially water-free state.

The present invention further relates to a new photosensitive material having a dye-donating substance that reacts with photosensitive silver halide upon heating in a substantially water-free state to release a hydrophilic dye.

The present invention particularly relates to a new method for obtaining dye images by transferring dyes released by heating to a dye fixing layer.

Photographic methods using silver halide have been used most widely since they have superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. 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 developing solution to a dry processing using heating, etc. It has been.

Heat-developable photosensitive materials are well known in the art, and for information on fully developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pages 553 to 555, and Eizo Information 4, published in April 1978. page, Neblet
ts Handbook OF Photograp
Hy and Reprography 7th Ed
, (Van No5trand Rejnhol
dC.

page 32-33 of U.S. Patent No. 3,152
No. 904, No. 3,301,678, No. 3,392.
No. 020, No. 3.4.57,075, British Patent No. 1.
No. 131,108, No. 1,167.777 and Research Disclosure Magazine June 1978 Issue 9-15
He-'; (RD-17029) Between the two bones.

Many methods have been proposed for obtaining color images. A method of forming a color image by combining an oxidized developer with a coupler is described in U.S. Pat.
, 531,286, a P-phenylenediamine reducing agent and a phenolic or active methylene coupler are described in U.S. Pat. ．． No. 761,270, P-aminophenol reducing agents are described in Belgian Patent No. 802,519 and Research Disclosure September 1975 3'l.
On page 32.

Sulfonamidophenolic reducing agents are also proposed in US Pat. No. 4,021,240, in which a combination of a sulfonamidophenolic 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 is a method to remove the silver image by liquid processing or to transfer only the two dyes to another layer, for example, 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 gold salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978, issue 54-5111, RD-16966. There is. With this method, it is difficult to suppress the release of dye in areas that are not exposed to light, and a clear image cannot be obtained, so it is not a common method.

Further, regarding the method of forming a positive color image by photosensitive silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue, pages 30-32 <RD-144
3s>, December 1976 issue of the same magazine, pages 14-15 (R
D-15227) 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 one 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 methods of forming color images using leuco dyes, for example, US Pat. No. 3,985,565 and US Pat.
．． 022. It is described in No. 6x7.

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.

Furthermore, the two or more methods generally require relatively long periods of time for development, and the resulting images have the drawbacks of high fog and low density.

An object of the present invention is to provide a new method of forming a dye image having a negative relationship to a silver image by heating in a substantially water-free state, and which is an improvement over the conventional light-sensitive materials. The aim is to resolve the shortcomings that it had.

The second object of the present invention is to provide a simple method for obtaining a color image, and the third object is to provide a color photosensitive material for heat development that can be used in the above method.

The above purpose is to reduce nitrogen atoms and A light-sensitive material containing a diffusion-resistant dye-donating substance having a heterocycle that causes a cleavage reaction of a heterocycle containing a sulfur atom or a selenium atom to release a mobile dye is exposed to water after or simultaneously with imagewise exposure. This is achieved by a method in which a mobile dye is formed into an image by heating it in a state that does not contain the dye.

Dye images of the present invention refer to multicolor and monochrome dye images;
In this case, the monochromatic image includes a monochromatic image obtained by mixing two or more types of dyes.

In the image forming method of the present invention, when heated in a state substantially free of water, a redox reaction occurs between the photosensitive silver halide having development nuclei and the reducing agent.2For example, in a negative emulsion, a silver image is formed in the exposed area. In the non-exposed area, the silver ions remaining inversely to the silver image act as catalysts to cleave the heterocycle containing nitrogen and sulfur atoms or selenium atoms in the dye-donating substance at high temperatures. This occurs and mobile dye is released resulting in a dye image that is in a negative relationship to the silver image.

When a negative emulsion is used, the image forming method of the present invention provides a positive image by moving this mobile dye to the dye fixing layer.

The above relationship is completely reversed in the case of a positive emulsion, with a mobile dye forming in the exposed area and an immobile dye forming in the non-exposed area.In the present invention, the above reaction occurs at high temperatures and in the absence of substantially water. is a feature. Here, high temperature refers to a temperature condition of 80°C or higher, and a dry state that does not substantially contain water refers to a state in which the water is in equilibrium with the moisture in the air, but there is no water supply from outside the system. . This kind of state is The theor
y of thephotographic p
rocess”4th Ed, (F, dited
by T.H.James, Macmill
an) described on page 374. 1O-3 shows a sufficient reaction rate even in a dry state that does not substantially contain water.
This can also be confirmed from the fact that the reaction rate of the sample vacuum-dried at u+)(g for 1 hour did not decrease).

Conventionally, the cleavage reaction was usually carried out in a liquid with a high pH of pr-rto or higher. However, the fact that the present invention does not achieve a high reaction rate in a dry state substantially free of water at high temperatures is an unexpected result based on previous knowledge of wet development at temperatures close to room temperature. It is.

The reaction of the present invention proceeds particularly well in the presence of an organic silver salt oxidizing agent and does not result in high image densities. Therefore, it is a particularly desirable embodiment to coexist an organic silver salt oxidizing agent.

The reaction of the present invention proceeds similarly in the presence of a soluble silver complex instead of silver ions.

The diffusion-resistant dye-donating substance used in the present invention, which releases a mobile dye by causing a ring cleavage reaction under high temperature conditions in the presence of silver ions or soluble silver complexes, is a compound represented by the following general formula (Δ). includes.

Z \ / C(A) 7・″, R2X-Dye Here, R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, or an aralkyl group, and the alkyl group and aryl group in the above groups The base portion is an alkoxy group, a hydroxyl group, a halogen atom, a cyano group,
Acyloxy group, alkoxycarbonyl group, acylamino group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, alkylsulfonylamino group, arylsulfonylamine group 1. It may be substituted with a ureido group or a substituted ureido group.

R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acylamino group, an alkyldio group, an arylthio group, a halogen atom, and -X-Dye as described below; The alkyl/14 and aryl group moieties in the group are alkoxy groups, water M! , halogen atom, cyano group, acyloxy group, alkoxycarbonyl group, acylamino group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, alkylsulfonylamino group, irisulfonylamino group, ureido group, substituted ureido It may be substituted with a group.

X represents a divalent linking group or a simple bond.

Y represents a sulfur or selenium atom.

Z represents an atomic group necessary to complete a 5-, 6-, or 7-membered heterocycle, and preferred heterocycles are thiazolidine, selenazolidine, benzothiazoline, and benzoselenapridine derivatives.

Preferably R1 is an alkyl group having 8 or more carbon atoms 1)y
e does not contain image-forming dyes or their precursors.

Preferred X is a divalent group not shown below.

-Rz- (hereinafter Rz represents an alkylene group).

-O-, -3-, -3O2-, -Nf(Co-.

-Rz-NHC,O-, -Rz-NH3O2.

-Rz-3O2NH-+ -Rz-CONH-.

-NHCONH-, -Bz (hereinafter Bz represents a phenylene group)-+ -BZ, -NHCC)-.

-Bz-NH3O-.

-Rz-Bz-NH'5O2-, -C.

Specific examples of the dye-donating substance used in the present invention are shown below, but the present invention is not limited thereto.

C0-NH-C2H.

( e□. H2□-n 0CH3 CH3 crawl 803K (CH213-OCI-13 CH3 example H3C-C-COOH morning) H2N 0 0H H 1 H2CH3 NHS O.

(40) ＼ l ・shiH3 Regarding the synthesis of the dye-donating substance used in the present invention,
U.S. Patent No. 3,719,489, 4.098783
No. and J, Am, Chem, Soc,, 101 No. 42
0 (1979), and can be synthesized according to these.

Two or more types of dye-providing substances used in the present invention may be used in combination. In this case, two or more types may be used in combination to create different hues, or three types may be used to create black.

The dye-providing substance used in the present invention is 10 mg to 1
It is appropriate to use it in a range of 5 g/m, more preferably from 20 mg to 1 Og/g.

The pigmented caries material can also be added to the same layer as the emulsion.

It is also possible to add ζ in adjacent order as long as they chemically influence each other.

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2,322.02.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. 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 fucrate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (eg acetyl tributyl citrate).

Benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl salacine-1-, dioctyl azelate), trimesic acid esters (e.g. i.
Organic solvents with a boiling point of about 30°C to 160°C 1. Lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvents and low boiling point organic solvents may be used in combination.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, a variety of surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, including 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 per 1 g of the dye-providing substance used.

Preferably it is 5g or less.

The reducing agents used in the present invention include the following.

Hydroquinone compounds (e.g. hydroquinone).

2.5-dichlorohydroquinone, 2-chlorohydroquinone), aminophenol, nol compounds (e.g. 4-aminophenol, N-methylaminephenol, 3-methyl-4-aminophenol, 3.5-dibromoaminophenol), catechol compounds (e.g. catechol, 4
- Cyclohexyl cartechol.

3-methoxycatechol, 4-(N-occudecylamino)catechol), phenylenediamine compounds (e.g., t
N, , N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-p
-phenylenediamine, N,'N,N'',N'-tetramethyl-p-phenylenediamine).

More preferable reducing agents include the following.

3-pyrazolidone compounds (e.g. 1-phenyl-3-hyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-
Phenyl, -3-pyrazolidone, ■-m-trilu-3-
Pyrazolidone, 1-”pt-true 3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis-(hydroxymethyl)-3-pyrazolidone, 1,4-di-methyl-3-virapritone,
4-methyl-3-pyrazolidone, 4,4-dimethyl-3
-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-chlorophenyl)
-4=methyl-3-pyrazolidone, 1-(4-tolyl)
-4-methyl-3-pyrazolidone, 1-'(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-3-pyrazolidone, 1-(3-tolyl)-3-pyrazolidone, 1-(3-trit)-4/, 4-dimethyl-3-pyrazolidone, 1-'(2-1-lifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3- pyrazolidone).

Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

Although the use of a silver halide solvent is preferred in the present invention, it is not essential since the ring cleavage reaction is assisted by the silver ions of the emulsion.

The silver halide solvent may be any of those hitherto known, such as sodium thiosulfate, potassium thiosulfate, sodium thiocyanate and uracil. Also, U.S. Patent No. 4.046. '568.

Silver halide solvent precursors described in US Pat. No. 4,107,176 can also be used.

Silver halides 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, particularly preferred silver halide is one containing silver iodide crystals in a part of the grains. Specifically, it is particularly preferable that silver halide exhibits a .xi. turn pattern when subjected to X-ray diffraction of silver halide.

Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary silver halide emulsions, the silver halide grains are entirely made up of completely mixed crystals. For example, in the case of a silver iodobromide emulsion, when X-ray diffraction of the grains is measured, .xi.-turns in silver iodide crystals and silver bromide crystals are not observed, but X-rays/e-turns are observed at positions corresponding to the mixing ratio.

Particularly preferred silver halides in the present application 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 a silver halide can be obtained, for example, by adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding thallium iodide.

Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination.

The average grain size of the silver halide grains used in the present invention is preferably from 0.00/μm to 70 μm, more preferably from o, ooi μm to 5 μm.

The silver halide used in the present invention may be used as it is, but it may also be used as a compound of sulfur, selenium, tellurium, etc., gold,
Chemical sensitization may be achieved by the use of r-hydrogen sensitizers such as platinum, palladium, rhodium and iridium compounds, reducing agents such as tin halides, or combinations thereof. For more information, see “The Theory of th”
o Photographic Process”
4' edition, by T. H. Jarnes! Chapter 1 page ~ 1
It is written on page 6.

A particularly preferred embodiment of the present invention is one in which an organic silver hydrochloride ratio agent is present, but when heated to a temperature of gO 0 C or more, preferably ioo 0C or more in the presence of photosensitive silver halide, Silver@
It forms the By coexisting with organic silver hydrochloride (arsenic), it is possible to obtain a photosensitive material that develops color at a higher density.

The silver halide used in this case does not necessarily have the characteristic of containing pure silver iodide crystals when silver halide is used alone, and is known in the art... can be used.

Examples of such organic silver salt oxidizing agents include the following.

It is a silver salt of an organic compound having a carboxyl group, and representative examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.

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,
Silver salt of capri/acid, silver salt of myristic acid, silver salt of palmitic acid, silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, oleic acid silver salts of adipic acid, silver salts of sepacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, silver salts of camphoric acid, etc. Furthermore, silver salts substituted with a halogen atom or a hydroxyful group are also effective.

Silver salts of aromatic carboxylic acids and other carfoquinol group-containing compounds include silver salts of benzoic acid, silver salts of 3゜terdihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, m
- silver salt of methylbenzoic acid, silver salt of p-methylbenzoic acid,
λ, silver salts of substituted benzoic acids such as silver salts of t-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, and silver salts of phthalic acid. silver salt, silver salt of terephthalic acid, silver salt of salicylic acid,
Silver salt of phenylacetic acid, silver salt of pyromellitic acid, silver salt of 3-carboxymethyl-coumethyl-hiro-thiazoline-2-thione described in U.S. Pat. No. 3,713,130, U.S. Pat. Examples include silver salts of aliphatic carboxylic acids having a thioether group, which are described in the specification of No. 330゜ttE.

Other examples include silver salts of compounds having mercapto groups or thio/groups and derivatives thereof.

For example, silver salt of 3-mercapto-+-phenyl-/, 2゜ψ-triazole, silver salt of λ-mercaptobenzimidazole, silver salt of -monomercapto-j-aminethiadiazole, silver salt of λ-mercaptobenzthiazole. , no (
Silver salts of thioglycolic acid and dithioacetic acid described in JP-A No. 2g22/, such as S-ethyl glycolamide) benzthiazole silver salt, S-alkyl (alkyl group having 72 to 22 carbon atoms) thioglycolic acetic acid, etc. silver salts of dithiocarboxylic acids, silver salts of thioamides, silver salts of tercarboxy-/-methyl-λ-phenyl-thiopyridine, silver salts of mercaptotriazine, silver salts of 2-mercaptobenzoxazole, such as the silver salts of , Silver Salt of Mercaptooxadiazole, U.S. Pat.

/λ3.27'A silver salts described in specification, for example /.

λ, Hiro-mercaptotriazole derivative 3-ami2! -benzylthio/, 2. Silver salt of Hiro-triazole, 3-( described in U.S. Pat. No. 3.30/47f)
2carboxyethyl)-≠-methyl-≠-thiazoline-lambda thione silver salt.

In addition, there are silver salts of compounds having imino groups. For example, the silver salts of benzotriazole and its derivatives described in Japanese Patent Publications Akihirohiro-30270 and Dohiroyoichi/RAIg,
For example, silver salts of alkyl-substituted benzotriazoles, such as silver salts of benzl=IJ azole, silver salts of methylbenzotriazole,! -Silver salts of rogane-substituted benzotriazoles, such as silver salts of chlorobenzotriazoles, silver salts of carboimidobenzotriazoles, such as silver salts of butylcarboimidobenzotriazoles, U.S. Patent ≠, 220
l, λ, ≠-triazole and/or
Examples include silver salts of -H-tetrazole, carbazole silver salts, saccharin silver salts, and imidazole and imidazole derivative silver salts.

Also Research Disclosure Vol/7θ, 797
Organometallic salts such as silver salts and copper stearate described in No. A/70.2, June 2007 are also organometallic salt oxidizing agents that can be used in the present invention.

Two or more kinds of organic silver hydrochloride ratio agents can be used.

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

When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver.

“The Theory of
thePhotographic Processes
s"3r'd Edition, page 10~/I
It is described on the LLg page.

For information on how to make these silver halides and organic silver salt oxidizing agents and how to mix both, please refer to Research Disclosure/7θλ issue and JP-A-Shoyu. -3λri2g, JP-A Shoj/
- Ko2j2, U.S. Patent No. 3°700, Kouyu g, Unexamined Japanese Patent Publication No. 4L/32. ! It is described in Japanese Unexamined Patent Application Publication No. 1987-172/1.

In the present invention, the total coating amount of photosensitive silver halide and organic silver salt oxidizing agent is approximately 100 ml in terms of silver. 〜〜1oy7y1
2 is appropriate.

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 contained alone or in combination. A hydrophilic material can be used as this ζ Ingu. Typical hydrophilic binders are transparent or translucent hydrophilic colloids, such as gelatin, gelatin derivatives, cellulose derivatives, and natural substances such as polysaccharides such as denopuno and gum arabic. and polyvinylpyrrolidone,
Includes 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.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring in these nuclei fused $L, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable.

These nuclei may be substituted on carbon atoms.For merocyanine dyes or complex merocyanine dyes, nuclei having a ketomethylene structure include pyrazolin-5-one nucleus, thiohydantoin nucleus, and 2-thioxazolidine-2,4-
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a deacylidine-2,4-dione nucleus, a rhodanine nucleus, a thioba, a rubituric acid nucleus, etc. can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231.6'58', U.S. Pat.
, No. 493,748, No. 2.5'03.776, No. 2
, No. 519,001, No. 2,912゜329, No. 3,
No. 656,959, 3. , No. 672.897, 3.
No. 694.217, No. 4゜025.349, No. 4,
Examples include those described in British Patent No. 046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, and Japanese Patent Publication No. 52-24844.

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 U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3.527.641, No. 3,617
．． No. 293, 3. No. 628゜964, 3,666
．． No. 480, No. 3,672.898, No. 3,679,
No. 428, No. 3゜703.377, No. 3,769.3
No. 01, No. 3.814,609, No. 3.83'/, 8
No. 62, No. 4,026,707, British Patent No. 1,344
．． No. 281, No. 1,507,803, Special Publication No. 43-4
No. 936, No. 53-12,375, JP-A No. 52-11
No. 0.618 and No. 52-109,925.

The sensitizing dye is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light, and
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (e.g. U.S. Pat. No. 3.7.43., 510)
(described in the above issue), cadmium salts, azaindene compounds, etc. Rice malt patent 3. 615. 6. '
No. 13, No. 3,615,641, No. 3,617. '2
No. 95, 3. The combinations described in '635,721 are particularly useful.

The support used in the present invention is one that can withstand the processing temperatures. Common supports include glass,
Not only paper, metal and their analogs are used;
Included are cellulose acetate film, cellulose ester film, polyvinyl acecool film, polystyrene film, polycarbonate film, polyethylene terephthalate film, and films or resin materials related thereto. Polyesters described in US Pat. No. 3,634,089 and US Pat. No. 3.7-25.070 are preferably used.

Various dye release aids can be used in the present invention. A dye release aid is a photosensitive silver halide and/or organic silver salt that promotes the redox reaction between an oxidizing agent and a reducing agent, or acts nucleophilically on a dye-donating substance in the dye release reaction. A base or a base precursor can be used to promote dye release. In the present invention, it is particularly advantageous to use the above-mentioned dye release aids to accelerate the reaction.

Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines,
Mention may be made of N-hydroquine alkyl-substituted aromatic amines and bis[p-(dialkylamino)phenylcomethanes. Also, US Patent No. 1, ≠10. t4t'
No. 7 contains tetramethylammonium betainoiodide,
Diaminobutane dihydrochloride is useful as organic compounds containing amino acids such as urea and t-aminocapronoic acid are described in US Pat. No. 3, SO6, ≠4L≠. The base precursor releases a basic component when heated. An example of a typical base precursor is British Patent No. 7.
It is written in g, ri≠ri number. 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, etc. be. US Patent No. 3゜2
λo, gtt (, guanidine trichloroacetic acid between the bones is particularly useful.Also, the aldonamides described in Japanese Patent Application Laid-Open No. 2003-120002 are preferable because they decompose at high temperatures to produce bases. used.

These dye release aids can be used in a wide variety of ways. The useful range is less than 50 g-7t, calculated as the weight of the coating film of the light-sensitive material, and more preferably 0.9 g.
07 weight ξ - cents to p.

It is in the range of percent.

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

General formula] In the above formula, A1. A2. A3. A4 may be the same or different, and each represents a substituent selected from a hydrogen atom, an alkyl group, a substituted alkyl group, an alkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a heterocyclic residue; , or A1 and A2 or A3 and A
4 may be connected to form a ring.

Specific example Toshiteha, 1-12NS02NH2°H2N50
2N(CH3)2. H2N502N(C2H5)2゜H
NSO'NHCH,)T2NS02N(C2H40H)
2゜2 2 3 CHNH30NHCH3.

３　　　　　2 The f-hybrid compounds mentioned above can be used in a wide range of applications.

A useful range is less than 2o weight·ξ-cents, more preferably 0.2o weight·ξ-cents, based on the weight of the coated film of the light-sensitive material.
/ to 15 weight (-cents).

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

A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are known particularly in the transfer printing of fibers, and NH4Fe(S04)2./, 2H20 and the like described in Japanese Patent Publication No. 0-♂g3g-O are useful.

Further, in the present invention, it is possible to use a compound that stabilizes the image at the same time as activation of development.

Among them, 2-
Intiuroniums represented by hydroxyethylisothiuronium trichloroacetate, U.S. Patent No. 3,
6 Otsuri, bisinthiuroniums such as /, g-(3,6-thioxaoctane)bis(isothiuronium trifluoroacetate) described in Otsu No. 70, West German Patent No. 2. /
12,7111, 2-amino-2-thiazolium trichloroacetate and λ-aminoterbromoethyl-2-thiazolium compounds described in U.S. Patent No. 0/2,2 Otsu θ. Thiazolium arsenic compounds such as trichloroacetate, U.S. Patent No. 010
, ≠ Compounds having α-sulfonylacetate as an acidic moiety such as bis(2-amino-2-+7zolium)methylenebis(sulfonylacetate) and λ-amino-2-thiazolium phenylsulfonylacetate described in No. 20, λ-carboxycarboxyamide' as the acidic moiety described in U.S. Pat.
-Motsu1hi compounds are preferred and used.

In the present invention, a heat disinfectant can be included.

As used herein, a "thermal solvent" is a non-hydrolyzable organic material that is solid at ambient temperature but exhibits a mixed melting point with other components at or below the heat treatment temperature used. Useful thermal solvents include f-hybrid compounds, which can serve as solvents for developing agents, and di-hybrid compounds, which are substances with a high dielectric constant and are known to accelerate the physical development of silver salts. Useful thermal solvents include the polyglycols described in U.S. Pat.
000 polyethylene glycol, derivatives such as oleate esters of polyethylene oxide, beeswax, monostearin, compounds with a high dielectric constant having a -5O2-1-C〇- group, such as acetamide, succinimide, ethylcal/(mate), etc. , urea, methylsulfonamide, ethylene carbonate, US Pat. No. 3.tly7
．． Polar substances between the bones, ≠-Hydroxybutanoic acid lactone, methylsulfinylmethane, tetrahydrothiophene-/,/-dioxide, Research Disclosure Magazine / July 2015 issue, 26- λg<-interosseous/, /Q-Decanediol, methyl anisate, biphenyl perate, etc. are preferably used.

In the case of the present invention, the dye-donating substance is colored;
Although it is not so necessary to incorporate irradiation-preventing substances or dyes into light-sensitive materials, in order to further improve the sharpness, Japanese Patent Publication Sho≠♂-36-2 and U.S. Pat. !3. ri, issue 2/, same 2. ! r2
7. O♂No.3, same λ, ri! It is possible to contain filter dyes and absorbent substances, which are described in various specifications such as No. 1, No. 17, etc. Preferably, these dyes are thermally decolorizable dyes, such as those disclosed in US Pat. Preference is given to dyes such as those described in t/, f, no. 113.2.

The photosensitive material used in the present invention may optionally 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, an intermediate layer, an AH layer, and a peel-off layer. It can contain layers and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes.

For example, saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol to polyethylene glycol/Po+), P-propylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amines or amides, polyethylene oxide compounds of Silico 7), glindol derivatives (e.g. Nonionic surfactants such as alkenylsuccinic acid polyglycerides, argylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates,
Alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl 7-acid ester, N-anru-N-alkyl taurine, sulfosuccinate, sulfoa, TI/Kilz
'IJ, t Anionic interface containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups, etc., such as oxyethylene alkyl phenyl ethers, polyoxy 7 ethylene alkyl phosphate esters, etc. Active agents: Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides and other amphoteric surfactants; Alkylamine salts, aliphatic or aromatic ψ-class ammonium salts, pyridinium, imidazo Cationic surfactants such as complex φ-class ammonium salts such as lithium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

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 5urf
acLant 5science Seriesvo
lume 1. Non1onic 5urfacta
nts (Edited by Martin J, 5
Chick.

Marcel Dekker Inc, /ri67)
, 3urface AcLive ELhylen
e QxideAdducts (3choufeld
Among the nonionic surfactants described in these documents, those satisfying the above conditions are preferably used in the present invention.

These nonionic surfactants may be used alone or as a mixture of two or more.

The polyethylene glycol type nonionosurfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably 90%.
Used below.

The light-sensitive 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.
l, 5ection B 3 Otsu (/Tata j), USP
2,4 Hiroza, to Hiro, usP 3. Otsu 7/, 2'A
7, Special public Akihiro≠-ta j0
It is listed in 3rd class.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3, 5=triacryloyl-hexahydro-5-)riazine, 1
．． 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-1-riazine, etc.), mucohalokene [J (mucochloric acid, mucophenoxychloroic acid, etc.), etc. Can be used alone or in combination.

Various additives include Re5earch])isclosure”VOI/70,
Additives such as additives described in No. 77029, June/Reg. 7g, etc., include edgers, sharpness-improving dyes, AH dyes, sensitizing dyes, matting agents, fluorescent whitening agents, and anti-fading agents.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the retention layer, intermediate layer, undercoat layer, backing layer, and other layers are prepared for each layer, and coated using the dipping method, air knife method, curtain coating method, or coating method. A photosensitive material can be prepared by sequentially coating the material on a support using various coating methods such as the hopper coating method described in Saimei Apparatus and drying it.

Furthermore, if necessary, two or more layers can be applied simultaneously by the methods described in U.S. Pat. .

Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources,
Also, a CRT light source, a fluorescent tube, a light emitting diode, etc. can be used as a light source.

The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to take portraits of people and landscapes using a trench camera. The printing from the original drawing may be done by overlaying the original drawing by contact printing, reflection printing, or enlargement printing.

It is also possible to output images taken by a video camera or the like or image information sent from a television station directly to a CRT or FOT, and then form the image on a heat-developable material using a contact lens or a lens, and then print it. It is possible.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various types of equipment. It is difficult to make an LED that effectively emits blue light. In this case, to reproduce a color image, three types of LEDs are used that emit green, red, and infrared light, and the parts of the sensitive material that are exposed to these lights emit yellow mazenota and cyan dyes, respectively. It should be designed to.

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

In addition to the above-mentioned method of directly attaching or projecting the original image, so-called image processing involves reading the original image illuminated by a light source using a light-receiving element such as a phototube or CCD, storing it in the memory of a computer, etc., and processing this information as necessary. There is also a method of reproducing this image information on a CRT and using it as an image-like light source, or directly causing the three types of LEDs to emit light based on the processed information for exposure.

In the present invention, after exposure of the photosensitive material, the resulting latent image is produced by exposing the element to a moderately elevated temperature, such as from about O.S seconds to about 300 seconds at about 0 to about 2J00C. It can be developed by heating.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.In particular, about /100
Temperature ranges from c to about 760' are useful.

The heating means may be a simple hot plate, an iron, a hot roller, a heating element using carbon or titanium white, or something similar.

In the present invention, a specific method for forming a color image by heat development is to move a hydrophilic mobile dye. For this purpose, the photosensitive material of the present invention has a photosensitive layer (1) on a support containing at least silver halide, optionally an organic silver hydrochloride, a dye donating substance which is also a reducing agent thereof, and a binder. and (1) a dye fixing layer that can receive the hydrophilic and diffusible dye formed in the layer (1).
U).

The above-mentioned photosensitive layer CI) and dye fixing layer (II) may be formed on the same support, or may be formed on separate supports. The dye fixing layer (1) and the photosensitive layer (I) can also be separated. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (II) or the photosensitive layer can be peeled off. In addition, the photosensitive layer (1)
When a photosensitive material coated on a support and a fixing material coated on a support are formed separately, the photosensitive material is imagewise exposed and heated uniformly, and then the fixing material can be layered to transfer the mobile dye to the fixed layer (II).

There is also a method in which only the photosensitive material (1) is imagewise exposed, and then the dye fixing layer (II) is superimposed and uniformly heated.

The dye fixing layer (n) can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful. In addition to the mordant, a base, a base precursor, etc., and a hot solvent may be included. In particular, when the photosensitive layer (1) and the dye fixing layer (II) are formed on different supports, it is particularly useful to include a base or a base precursor in the fixing layer (IT).

The polymer mordant used in the present invention is a polymer containing a secondary or tertiary amine group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cationic group, etc., and has a molecular weight of 000-λOo, ooo , especially 10.0
00~so, ooo.

For example, U.S. patent yu, ri≠, and yuotsu ψ, same yu.

≠g ri, 1I-3θ issue, same 3, /II-do, 06/ issue, same 3.7! t, III-vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in Saimei Seki et al.; U.S. Patent No. 3. Otsu 2ta, Otsu 7≠ issue, same 3. ! ! ;ri, Ori No. 6, same≠, /λg.

331, British Patent/, 277, ≠53, etc., a polymer mordant capable of crosslinking with gelatin, etc.;
US Patent 3. 3g, 9? '! No. i, same, 2,7.
2/, No. 152, No. 2,77g, No. Otsu No. 3, Tokukai Akihiro-//No. 32 Kog, same as left '+ -/ 41-Yuri λri No., same as left≠-/ Specification of No. 21027 Aqueous sol-type mordant disclosed in U.S. Patent No. 3. A door and a water-insoluble mordant disclosed in org; US Pat.
g, 971. A reactive mordant capable of forming a covalent bond with a dye disclosed in the specification of US Pat. No. 3,700, Otsuri No.
71g, No. 1 Oj, 3. B t1. ．． 2.4' and No. 2,
Same 3. 'A, Iza.

70 Otsu No. 3. Tata 7.0 Otsu No. 31.27/,
/'I-7, 3,. 27/, ll1-g issue, Tokukai Sho! ;0-7/33 issue, same! r3-303.2g issue,
Tata 2-/Tata 5.2, Tata j3-7 No.J, Tata J3
Mention may be made of the mordant disclosed in the specification of No.-102ψ.

Other US Patents 2. t7j, No. 3/A, same λ.

ll2. /! Mention may also be made of the mordants described in Specification iA.

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) A group having an ammonium group and capable of covalently bonding to seratin (for example, an aldehyde group, a chloroalkanoyl group, a chloroalkyl group), a vinyl carbonyl group,
hyridinium propionyl group, vinyl carbonyl group, alkylsulfonoxy group, etc.) For example, C=OC-O 1 (2) Repeating units of a monomer represented by the following general formula and other ethylenically unsaturated monomers reaction product of a copolymer consisting of a cross-linking agent (e.g. hahisalkanosulfonate, hisarenesulfonate).

Aryl group, also b At least R3-R5 λ together Peter -C may also form a ring.

X: anion (the above alkyl groups and aryl groups include substituted ones) (3) Polymer X represented by the following general formula: about 0, . 2
t to about t molar coefficient y: about θ to about θ molar coefficient 2: about 10 to about t molar coefficient A: monomer having at least two ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated monomer Q: N , P bb R, R2, R3: alkyl group, cyclic hydrocarbon group, or at least two of R to Rb3 may be combined to form a term. (These groups and rings may be substituted.) (4) Copolymer X consisting of (a), , (b) and (C): hydrogen atom, alkyl group or no loge/atom (
Alkyl groups may be substituted. ) (b) Acrylic ester (C) Acrylonitrile (5) A water-insoluble polymer having //3 or more repeating units represented by the following general formula b b b R, R2, R3: Each represents an alkyl group. Mine. (The alkyl group may be substituted.) X: Anion As the gelatin used in the mordant layer, various known gelatins may 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 determined by those skilled in the art according to the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process used for further processing. can be easily determined,
Kiruga, mordant layer 1/gelatino and heat-7) x2o/几~g
o/i0c** ratio), mordant layer 11 coating amount is O1 evening~gy
Force used at /m2; preferred.

The dye fixing layer (II) may have a white reflective layer. For example, gelatin/
A layer of titanium dioxide dispersed in 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 fixative 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.

For dye transfer from the photosensitive layer to the dye fixed layer.

Dye transfer aids can be used.

In a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, and an inorganic alkali metal salt is used as the dye transfer aid. Further, a low boiling point solvent such as methanol, N,N-dimethylbormamide, acetone, diisobutyl ketone, or a mixed solution of a low boiling point solvent such as chlorine and water or a basic aqueous solution is used. The dye transfer aid may be used by moistening the image-receiving layer with the transfer aid.If the transfer aid is incorporated into the light-sensitive material or dye fixing material, there is no need to supply the transfer aid from the outside. The above transfer aid may be incorporated into the material in the form of crystal water or microcapsules, or may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye-fixing material.

The hydrophilic thermal solvent may be incorporated into either of the photosensitive paulownia material (1) or the element-fixing material (2), or both of the photosensitive paulownia material (1) and (2). Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer or a dye fixing layer, but examples of hydrophilic heat solvents preferably incorporated in the dye fixing layer and/or its adjacent layer include ureas,
Pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Example 1 This article describes how to make a silver iodobromide emulsion.

Dissolve 40 g of gelatin and 26 g of KBI in 3000 ml of water. This solution is kept at 50°C and stirred. Next, silver nitrate 3
4. g dissolved in 200 ml of water was added to the above solution over 10 minutes.

Thereafter, a solution containing 3.3 g of KI dissolved in 100 ml was added over 2 minutes.

The pH of the silver iodobromide emulsion thus prepared is adjusted, and the emulsion is allowed to settle to remove excess salt.

Then adjust the pH to 6.0 and collect! 400 g of silver iodobromide emulsion was obtained.

Next, we will discuss how to make a benzotriazole silver emulsion.

Dissolve 28 g of gelatin and 1:2 g of benzotriazole in 3000 ml of water. This solution is kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water is added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion is adjusted, and excess salt is removed by settling. Thereafter, the pH was adjusted to 6.0, and a yield of 400 g of benzotriazole was obtained.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

5g of yellow dye-donating substance (40) succinic acid-2
-Ethyl-hexyl ester sulfonic acid soda 0.5g
, Weigh out 5 g of treble resin phosphate (TCP), add 30 ml of ethyl acetate, and dissolve by heating to about 60° C. to form a homogeneous solution. This solution and 100 g of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer for 10 minutes at 10.00 ORPM.

This dispersion liquid is called a dispersion of a dye-providing substance (40).

Next, how to make photosensitive materials A and B will be described.

Photosensitive material A (a) 25 g of the above silver iodobromide emulsion (b) 33 g of dispersion of dye-donating substance (40) (c) 5% aqueous solution of compound AA 5 ml (d) 10% ethanol solution of guanidine trichloroacetic acid 12 ml
(e) 10% methanol volume of 1-phenyl-4,4-dimethyl-3-virazolidone? Pz0ml or more (a) to (e) were mixed and dissolved, and then coated on a polyethylene terephthalate film to a wet film thickness of 30 μm and dried. Furthermore, on top of this, the following four types are added as a protective layer: (a) 35 g of 10% gelatin aqueous solution
(b) 10% ethanol of guanidine trichloroacetic acid
Volume: 5ml (c) Succinic acid-2-
A 1% aqueous solution of sodium ethyl-hexyl ester sulfonate (ml) (d) A mixed solution of 56 ml of water was applied to a wet film thickness of 25 m, and then dried to prepare a photosensitive material A.

Photosensitive material B is (a) benzotriazole silver emulsion 10 g (b) silver iodobromide emulsion 2' Og (C) dispersion of dye-providing substance (7) 33 g (d) 5% aqueous solution of compound AA 5 ml (e ) Guanidine trichloroacetic acid 1
0% ethanol solution 12.5ml (f)1
-phenyl-4,4-dimethyl-3-virazolidone 1
After mixing and melting 10ml of 0% methanol solution, it was applied onto a polyethylene terephthalate film to a wet film thickness of 30m, and then dried. The protective layer was applied in the same manner as Coating A.

Next, we will discuss how to make a dye fixing material.Poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (Ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) 1'O'g It was dissolved in 20 On+1 water and uniformly mixed with 100 g of 10% lime-treated gelatin'. This mixed solution was uniformly applied onto a paper substrate laminated with polyethylene in which titanium dioxide was dispersed to a film thickness of 90 μm. After drying, this sample is used as a dye fixing material having a mordant layer.

The above photosensitive coatings A and B were 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 130C.

Next, the dye-fixing material is immersed in water, and the film surface of the wet dye-fixing material and the photosensitive coating material A that has been heat-treated are
, B were superimposed so that their film surfaces were in contact with each other. After that 80
After heating for 6 seconds on a heat block at .degree. C., the dye-fixing material 9 was peeled off from the light-sensitive material, and a yellow color image negative to the silver image was obtained on the dye-fixing material. The density of this negative image against blue light is determined by the Macbeth reflection density needle (RD51).
The results measured using 9) are shown in the table below.

r -77---Bottom-1, -1 1 exposure I maximum 1 minimum 1 gradation (exposure 1 1 material 1 density 1 #i degree 1 amount 10 times vs. 11 No. 1
1 1L, te) 1F----10---10-
−−−+ −−−−−@l A l 1.73
+ 0.621 1.3 l to--, +,-
-10--1111--+l B' 11.98
10.501 1.4 1L-111--Eng.
-Top-J Example 2 Exactly the same as the photosensitive material B of Example 1 except that 5 g of each of the dye-donating substances (1), (39) was used instead of the dye-donating substance (40) of Example 1. Photosensitive materials C and D were prepared by straining and subjected to the same treatment as in Example 1, and the results shown in the table below were obtained.

"-111 lower 11--1-77-"1 1 Sensitivity 1 Dye-donating property 1 Maximum 1 Minimum 11 Materials I No. 1 concentration 1 concentration 11 NO+,, l11 1------ 10- −−−−−−−10−−−10−−−@
I C+ (1) 11.85
10.57 1 to--= 10------'--+
-----(-1τ-HI D l (39)
11.91 10.49 1 Shiichi---Eng---
The color image had a negative relationship to the silver image.

Example 3 Instead of the dye fixing material used in Example 1, another dye fixing material was prepared by the method described below.

Poly(methyl acrylate-N,N,N-1-rimedyl-N-vinylhensylammonium chloride) (methyl acrylate and vinylhensylammonium chloride 1
The ratio of 1:1) was melted in 200 ml of water and mixed uniformly with 100 g of 10% lime-treated gelatin. Pour this mixture onto polyethylene terephragm for 90 minutes.
It was applied uniformly to a wet film thickness of μm.

After mixing and melting the following (k) to (0) on this film, the mixture was uniformly coated on a 60 μm thick film and dried. below.

This second layer is called a hydrophilic thermal solvent layer.

(k) Urea (hydrophilic heat solvent) 4g (1) Water
1010 m1 (10% of polyvinyl alcohol (genification degree 98%)
Weight% water 12g (n) Compound AA100
mg (0) 5% aqueous solution of sodium dodecylhenzenesulfonate 0.5ml Photosensitive materials A and B of Example 1
was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb, and then heated uniformly for 20 seconds on a heat block heated to 140°C.

Next, after bringing the coated surfaces into close contact with the above dye fixing material, the peeling process was carried out at 120°C for 30 minutes with a peel block.
Heated for seconds.

When the dye-fixing material was peeled off from the light-sensitive material, a positive yellow image was obtained on the dye-fixing material.

Patent applicant: Fuji Photo Film Co., Ltd. 327

Claims (1)

[Claims] At least a photosensitive silver halide, a binder, a reducing agent capable of reducing the photosensitive silver halide under high temperature conditions, and a nitrogen atom, a sulfur atom, or a selenium atom under a high temperature condition in which silver ions or soluble silver complexes are present on the support. After or simultaneously with imagewise exposure, a light-sensitive material having a diffusion-resistant dye-donating substance having said heterocycle which undergoes a cleavage reaction of a heterocycle containing said heterocycle to release a mobile dye is subjected to a cleavage reaction of a heterocycle containing said heterocycle in a substantially water-free state. A method of heating and forming mobile dye into an image.