JPS61153638A - Dye fixing material - Google Patents

Abstract

PURPOSE:To obtain a dye fixing material having superior light stability and giving a color image with little light stain by diffusing an imagewise distributed diffusible dye at a high temp. and incorporating an ultraviolet absorber into a layer fixing the diffused dye and/or a layer adjacent to the fixing layer. CONSTITUTION:A diffusible dye is imagewise distributed preferably by subjecting a photosensitive material having photosensitive silver halide, a compound which produces or releases the diffusible dye and a binder on a support to imagewise exposure and heating in succession or at the same time. When the photosensitive silver halide is reduced at a high temp., the compound produces or releases the diffusible dye in proportion or inverse proportion to the reaction. An ultraviolet absorber to be used may be an aryl substituted benzotriazole compound, a 4-thiazolidone compound, a benzophenone compound or cinnamic ester, and it is incorporated by 0.01-40wt%, preferably 0.1-10wt% of the amount of a mordant.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background Technical Field of the Invention The present invention relates to a dye-fixing material having a layer for diffusing image-wise distributed diffusible dyes under high temperature conditions and fixing the diffused dyes.

Prior art and its problems Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. It is used in

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. has been done.

Heat-developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, see, for example, Photo Engineering Basics 1id (published by Korosu Publishing Co., Ltd. in 1979), pages 553-5.
Page 55, April 1978 video information page 40, Ne
bullets Hanclooka, -IPhotog
raph2 and reprograpby 7t
h Ed, (Van Nostrand Re1nho
ld Company, pp. 32-32, U.S. Patent No. 3.152,904, No. 3°301.6
No. 78, No. 3.392, o2o No. 3.457.0
No. 75, British Patent No. 1゜131.108, No. 1.16
7.777 and Research Disclosure Magazine 1
978, June issue, pages 9-15 (RD-17029)
It is described in.

Regarding how to obtain color images by heat development,
Many proposals have been made. U.S. Patent No. 3.531,
No. 286, No. 3, No. 761.270, No. 4.0
No. 21.240, Belgian Patent No. 802,5194.
Research Disclosure Magazine September 1975 Issue 31
．． On page 32, etc., a method of forming a color image by combining an oxidized form of a developer with a coupler and various developers used for its removal are described.

In addition, a nitrogen-containing heterocyclic group is introduced into the dye, a silver salt is formed, and the dye is produced by heat development! This letter is from Research Disclosure magazine, May 1978 issue, pages 54-58 (RD-
16966).

Further, regarding the method of forming a positive color image by approximately thermal silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433).
), December 1976 issue, pages 14-15 (HD-15
227) and U.S. Pat. No. 4,235,957, useful methods for bleaching dyes are described.

Further, regarding methods of forming color images using leuco dyes, for example, U.S. Pat.
, No. 022,617, etc.

However, in these color image forming methods, during long-term storage of the formed color image, discoloration and coloring of the white background occur due to coexisting silver halide, silver complex, developer, etc. A new method of forming a color image by heat development, which improves these drawbacks, is disclosed in JP-A-57-179840, JP-A No. 57-186774,
No. 57-198458, No. 57-207250, No. 58-58543, No. 58-79247, No. 58-
No. 116537, No. 58-149046, No. 59-4
No. 8764, No. 59-65839, No. 59-7104
No. 6, No. 59-87450, No. 59-88730, etc.

When photosensitive silver halide and/or softener silver salt is reduced to silver by heat development, a mobile dye is generated or released in response to or inversely to this reaction, and this mobile dye is This is a method of transferring to a dye fixing element.

Although these methods provide excellent color images, they have drawbacks such as poor light fastness of color image dyes due to high temperature conditions and the occurrence of light stains, and improvements in these points are desired. .

II. OBJECTS OF THE INVENTION The object of the present invention is to diffuse diffusible dyes distributed in image form under high temperature conditions and fix the diffused dyes.
An object of the present invention is to provide a dye-fixing material that has excellent light fastness and provides color images with little light stain.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention provides a dye fixing material having a layer for fixing the diffusible dye distributed in an image under high temperature conditions and for fixing the diffused dye. This is a dye fixing material characterized by containing an agent.

Among the methods for distributing the diffusible dye in an imagewise manner, a preferred method is to apply at least photosensitive silver halide on the support, and when the photosensitive silver halide is reduced at a high temperature, this reaction can be supported or reversed. Examples include a method in which a light-sensitive material containing a binder and a compound that generates or releases a correspondingly diffusible dye is heated after or simultaneously with the imagewise exposure.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The dye fixing material of the present invention contains an ultraviolet absorber.

Examples of ultraviolet absorbers include benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,53
3,794), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,
352.

681), benzophenone compounds (for example, those described in JP-A-46-2784), and cinnamic acid ester compounds (for example, U.S. Pat. No. 3,705,805, U.S. Pat. No. 3,707).

No. 375), butadiene compounds (such as those described in U.S. Pat. No. 4.045.229), or benzoxazole compounds (such as those described in U.S. Pat. No. 3.375).
700.455) can be used. Furthermore, benzylidene malonate compounds and oxamide compounds can also be used. Additionally, U.S. Patent No. 3.49
Those described in No. 9.762 and JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used.

Specific examples of the ultraviolet absorbent used in the present invention are shown below.

Benzophenones (1) 2,4-dihydroxy-benzophenone (2) 2
-Hydroxy-4-methoxy-benzophenone (3) 2.2'-dihydroxy-4-methoxy-benzophenone (4) 2-hydroxy-4-n-octyloxy-benzophenone (5) 2-hydroxy-4-iso-octyl Oxy-
Benzophenone (6) 2-hydroxy-4-dodecyloxy-benzophenone Benzotriazoles (7) 2- (2'-hydroxy-5'-methylphenyl)-benzotriazole (8) 2- (2'-hydroxy-3' , 5'-G-t
-butylphenyl)-benzotriazole (9) 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-10 rubenzotriazole (10) 2- (2'-hydroxy-3 ', 5'-G-
t-butylphenyl)-5-chlorobenzotriazole (11) 2-(2'-hydroxy-3',5'-di-
t-amylphenyl)-benzotriazole (12) 2- (2'-hydroxy73'-di-L-amylphenyl)-benzotriazole (13) 2- (
2'-hydroxy-3'-s-butyl-5'-t-butylphenyl)-benzotriazole (14) 2- (2'-hydroxy-5''-t-butylphenyl)-benzotriazole (15) 2- (
2'-Hydroxy-5-t-octylphenyl)-benzotriazole (16) 50% of 2-[((2'-
Hydroxy-3'-t-butyl-5'-(2N-n-octyloxy-carbonyl)-ethyl)phenyl]-5
-chlorobenzotriazole and 50% 2-[(2
'-Hydroxy-3'-71butyl-5'-(2N-
Mixture of ((2N'-ethylhexyloxy)carbonyl)ethyl)phenyl]-5-chlorobenzotriazole (17) 2-[2'-hydroxy-3',5''-
Di(α,α-dimethylbenzyl)-phenyl]-benzotriazole benzylidene malonates (18) Methyl-2-carphokydimethyl-3-(4′-
methoxyphenyl)-acrylate (19) ethyl-caffleboxyethyl-3-(4'-methoxyphenyl)-
Acrylate (20) hexadecyl-2-cyano-3-
(4-Methylphenyl)-probeonate salicylates (21) p-octylphenyl salicylate (22) phenyl salicylate (23) t-/tylphenyl salicylate monobenzoates (24) resorcinol mono Benzoate (25)3.
5-di-t-butyl-4-hydroxy-benzoic acid hexadecyl ester oxamides (26) 5-t-butyl-2-ethoxy-2'-ethyloxanilide (27) 2-ethoxy-2'- Ethyloxanilide aminobutadienes (28) octyl-5-(N,N-diethylamino)-
2-benzenesulfonyl-2,4-pentagenoate (29) Methyl-5-(N,N-di-n-hexylamino)-2-cyano-2,4-pentagenoate (30) 4- (N, N-diH-hexylamino)-
1,1-dicyano-1,3-butadiene (31) 4-
(N,N-diethylamino)-1-acetyl-1-p-
) Lylsulfonyl-1,3-butadiene (32) 4- (N,N-diethylamino)-1,1-
Diacetyl-1,3-butadiene(33)ethyl-5-
(N,N-diethylamino)-2-acetyl-2,4-
Pentagenoate (34) methyl-(N,N-dimethylamino)-2
-Methoxycarfoquinyl-2,4-pentadienoate and others (35) 2,4-di-butylphenyl-3,5-t-phthyl-4-hydroxybenzoate (36) 3,5-di-1 Butyl p-hydroxybenzoic acid (37) di(1,2,2,6,6-bentamethyl-4-
piperidinyl)-butyl (3',5'-t-butyl-4-hydroxy-benzyl) malonate (38) bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (39) bis( 1,2,2,6,6-bentamethyl-4
-piperidinyl) sebacate (40) butanetetracarboxylic acid tetra(2°2.6.
6-tetramethyl-4-piperidinyl) ester The above-mentioned ultraviolet absorber diffuses the imagewise distributed diffusible dye under high temperature conditions, and forms a layer that fixes the diffusing dye and/or a layer adjacent thereto (e.g. (protective layer).

As the layer for fixing the diffusing dye (hereinafter referred to as 1 dye fixing layer), it is preferable to use the mordant described below, but polyvinylpyrrolidone or the like may also be used. etc. may be used together.

The amount of the ultraviolet absorber added may be any ratio, but preferably 0.01 to 40% by weight, more preferably 0.1 to 40% by weight, based on the mordant (polyvinylpyrrolidone, etc. when using polyvinylpyrrolidone). It is 10% by weight.

However, if it is added to both the dye fixing layer and its adjacent layer, the total amount is used.

In order to add the ultraviolet absorber used in the present invention into the dye fixing material, the following dispersion method (item ii in JP-A-57-157245 can be applied).

For example, high-boiling organic solvents that are substantially insoluble in water [e.g.
Alkyl esters of phthalic acid (e.g. dibutyl phthalate, dioctyl phthalate, etc.), trimellitic acid esters (e.g. tri-octyl trimellitate)
, aromatic ethers, phosphoric acid esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl citric acid) tributyl)
, an alkylamide (for example, N,N-diethyl laurylamide), etc., and the resulting solution is emulsified and dispersed in an aqueous solution of a hydrophilic organic colloid (for example, as described in US Patent No. 2.
322.027, etc.), water-insoluble high-boiling organic solvents that are further used in combination with auxiliary solvents (e.g., water-soluble solvents such as methanol, acetone, methyl cellosolve, and substantially water-insoluble solvents such as ethyl acetate and butyl acetate). (see, for example, U.S. Pat. a water-insoluble high-boiling organic solvent; a substantially water-insoluble low-boiling organic solvent;
The present invention can be carried out by adding it to an aqueous polymer latex dispersion or a polymer latex containing a woody colloid. A latex dispersion method in which a compound is dispersed in a state impregnated into polymer latex particles (for example, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59942, Japanese Patent Publication No. 51-59943), and a method in which an ultraviolet absorber is added to water. Dissolved in a soluble solvent (e.g. acetone, methyl cellosolve, methanol, ethanol, etc.)
A method in which the dye fixing material is directly dispersed in a hydrophilic organic colloid coating solution, or a method in which the ultraviolet absorber itself is oily at room temperature is emulsified and dispersed in a hydrophilic organic colloid solution and then added to the coating solution. I can list the first prize. Particularly preferred is a method in which the material is dissolved in a substantially water-insoluble high-boiling organic solvent, or in combination with an auxiliary solvent, and then emulsified and dispersed in an aqueous solution of a hydrophilic organic colloid, or a latex dispersion method.

The ultraviolet absorber used in the present invention is emulsified and dispersed using about 0.1 to about 10 ml of a high boiling point organic solvent, preferably 0.2 to 4 ml, of an IgM emulsion dispersion solution. Also, the weight ratio of the ultraviolet absorber and the dispersed polybo latex was set to about 0.
A range of 1 to about 10 g, preferably 0.2 to 4 g, is used to disperse the latex.

The dye fixing material of the present invention has a dye fixing layer that fixes a diffusible dye that diffuses under high temperature conditions, and as mentioned above, it can be arbitrarily selected from commonly used mordants, polyvinyl pyrotone, etc. However, it is preferable to use a mordant, and among them, a polymer mordant is particularly preferable.
Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Polymers containing a vinyl nitrate unit having a tertiary amine group are described in i Specific examples of polymers containing units include British Patent Nos. 2,056,101, 2,093,041, and 1,594.

No. 961, U.S. Patent No. 4,124,386, U.S. Patent No. 4,
No. 115, 124, No. 4, 273.

No. 853, No. 4.450.224, JP-A-48-2
8.225 etc.

Preferred specific examples of polymers containing one vinyl unit having a quaternary ammonium salt include U.S. Pat. Nos. 3,709,690, 3,898,088, and 3,958.

No. 995, Japanese Patent Application No. 58-166135, No. 58-18
No. 9012, No. 58-232070, No. 58-232
No. 072 and No. 59-91620.

The mixing ratio of the polymer mordant and gelatin 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 mordant, type a and composition of the polymer mordant, and the image forming process to be used. However, the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio),
The amount of mordant applied is preferably 0.2 to 15 g/m', preferably 0.5 to 8 g/m'. The molecular weight of the polymer mordant of the present invention is 1゜ooo-i, oo
o, ooo, especially 10°000 to 200.000 are preferred.

When the polymer of the present invention is used as a mordant, the dye transfer density can be increased by using metal ions in the dye fixing material. The metal ions are added to the mordant layer containing the mordant, or to the adjacent upper or lower layer.

The metal ion used here is desirably colorless and stable against heat and light, i.e., Cu2+
, Zn2+, N i 2+, p j 2+, pd2+,
Polyvalent ions of transition metals such as Co3+ are preferable,
ZnZ+ is particularly preferred; this metal ion is usually in the form of water-soluble compounds, such as ZnSO4, Zn(CH3
CO2)2, and the amount added is 0-01 to 5
g/rrI', preferably O51-1, 5 g/rr
It is f.

The photographic element of the present invention is composed of a light-sensitive material that forms or releases a dye upon heat development and, optionally, a dye-fixing material that fixes the dye.

In particular, in systems that form images by diffusion transfer of dyes, a light-sensitive material and a dye-fixing material are essential, and in a typical form, the light-sensitive material and dye-fixing material are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support.

In the present invention, a configuration in which the coating is applied separately on two supports is preferred, and a peelable type described below is particularly preferred.

There are two types of forms in which a light-sensitive material and a dye-fixing material are formed on separate supports: one is a peelable type and the other is a peelable type. In the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive material and the coated surface of the dye-fixing material are overlapped, and after the transfer image is formed, the photosensitive material is immediately peeled off from the dye-fixing material. Depending on whether the final image is of a reflective type or a transmissive type, the support for the dye fixing material can be selected from an opaque support or a transparent support.
In addition, a white reflective layer may be coated if necessary. In the case of the latter type that does not require peeling, a white reflective layer is interposed between the photosensitive layer in the photosensitive material and the dye fixing layer in the dye fixing material. This white reflective layer may be coated on either of the photosensitive material 1 and the dye-fixing material.The support for the dye-fixing material must be a transparent support.

A typical example in which the light-sensitive material and the dye-fixing material are coated on the same support is one in which there is no need to peel the light-sensitive material from the image-receiving material after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective layer/photosensitive layer.

Another typical form in which a light-sensitive material and a dye-fixing material are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
, Canadian Patent No. 674°082, U.S. Patent No. 3,73
As described in No. 0,718, there is a form in which part or all of the photosensitive material is peeled off from the dye fixing material, and a peeling layer is coated at an appropriate position.

The photosensitive material or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, the photosensitive material used in the present invention consists of at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to distinctly different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, and a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, a blue-sensitive emulsion layer, a combination of an A & sensitive emulsion layer and an infrared-sensitive emulsion layer, a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer There are combinations of emulsion layers. Note that the infrared light-sensitive emulsion layer refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 740 nm or more.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

Each of the above emulsion layers and/or the non-photosensitive woody colloid layer adjacent to each emulsion layer has a dye-donating substance that releases or forms a yellow woody dye and a magenta woody dye. Alternatively, it is necessary to contain at least one of a dye-providing substance that forms a cyan hydrophilic dye and a dye-donating substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive woody colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form woody dyes of different hues. be. If desired, two or more dye-providing substances having the same hue may be used in combination. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from this emulsion layer. In addition, auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matting agent layer can be provided as necessary.

In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion. In addition, this protective layer may contain a mordant, a UV absorber, etc.
Each of the protective layer and the intermediate layer may be composed of two or more layers.

The middle layer also contains a reducing agent to prevent color mixing.

A UV absorber and a white pigment such as T i O2 may be included. The white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

The dye fixing material used in the present invention is a mordant.

Alternatively, if at least one layer containing polyvinyl pyrotone or the like is disposed and the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, polyvinylpyrrolidone, or the like, if necessary.

In addition to the above-mentioned layers, the dye fixing material used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye migration, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, and an antifade agent to increase dimensional stability. A dispersed vinyl compound, a fluorescent whitening agent, etc. may also be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, dextrin, pullulan,
Synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, etc. are used. Especially gelatin,
Polyvinyl rule call is valid.

The amount of the hydrophilic binder added is 0.1 to 20 g/go,
Preferably it is 1 to Log/go. In addition to the above, the dye fixing material may have a reflective layer containing a white pigment such as titanium oxide, a neutralization layer, a neutralization timing layer, etc., depending on the purpose. The above-mentioned reflective layer, neutralization layer, which may be coated in the material,
The configuration of the neutralization timing layer is described, for example, in U.S. Pat.
No. 83,606, No. 3.362,819, No. 3
, 362.

821, Canadian Patent No. 3,415,644, Canadian Patent No. 9
No. 28,559, etc.

Furthermore, it is advantageous for the dye fixing material of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside (Japanese Patent Laid-Open Nos. 57-154232, 58
-108533, 59-48755, 59-5
No. 2237, U.S. Patent No. 4°433.048 and European Patent No. 100°984);
, 5 p-ra or less, diameter at least 0, 81 Lm
tabular grains with an average aspect ratio of 5 or more (such as U.S. Pat. A monodispersed emulsion with a near uniformity (
JP 57-178235, JP 58-100846, JP 58-14829, International Publication No. 83102338A
No. 1, European Patent $64,412 A3 and rH1 No. 83
377AI) may also be used in the present invention. Two or more types of silver halides with different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used together. Two or more types of monodispersed emulsions with different grain sizes are mixed to adjust the gradation. You can also.

The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside one grain. Direct inversion emulsions combining emulsions and nucleating agents can also be used.

In the present invention, an organic metal salt that is relatively stable to light can be used together with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance. Among such organic metal salts, JaIR salts are particularly preferably used. When an organic metal salt is used in combination in this way, when the heat-developable photosensitive material is heated to a temperature of 80°C or higher, preferably 100°C or higher, the organic metal oxidant also undergoes redox using the silver halide latent image as a catalyst. It is thought that they are involved.

Organic above! Organic compounds that can be used to form the acidifying agent include aliphatic or aromatic carboxylic acids;
Examples include thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, 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, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable.
These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

In the present invention, when photosensitive I\silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a diffusible dye in response to or inversely to this reaction, i.e. Contains a dye-donating substance.

The diffusible dye is preferably one that forms an image when the photosensitive material used in the present invention is heated after imagewise exposure or simultaneously with imagewise exposure.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers are given in, for example, T. H. James, “The
ory of the photography
c precess”4th, Ed, , 291
~334 pages and 354-361 pages, Makoto Kikuchi, "Photochemistry" 4th edition (Kyoritsu Publishing) 284-295
It is described in detail on the page.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds can be found in Research Disclosure Magazine, 1978, 5.
Monthly issue, pages 54-58, (HD-16966), etc.

Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances. Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No. 4.235.957.
No., Research Disclosure Magazine, April 1976 issue, pages 30-32 (HD-14433).

Also, U.S. Patent Nos. 3,985,565 and 4,022
, No. 617, etc., can also be mentioned as an example of the dye-donating substance.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner.

This type of compound can be represented by the following general formula (LI).

(Dye - Correspondingly, a difference is caused in the diffusivity of the compound represented by (Dye-X)n-Y, or Dye
represents a group having the property of releasing Dye and causing a difference in diffusivity between the released Dye and (Dye-X)n-Y, where n represents 1 or 2, and when n is 2, ,
The two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
issue.

Same No. 3,362,819.

It is described in the same No. 3,597,200, the same No. 3.544.545, the same No. 3.482.972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was disclosed in Japanese Patent Application Laid-open No. 51-63
No. 618, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring is disclosed in JP-A No. 49/1989.
No. 111,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

In addition, in these methods, development and dye release or diffusion occur in parallel, making it very difficult to obtain images with a high S/N ratio. Therefore, in order to improve this drawback, dye release A method has also been devised in which the compound is made into an oxidized form that does not have the ability to release a dye, is made to coexist with a reducing agent or its precursor, and after development is reduced by the reducing agent that remains unoxidized to release a diffusible dye. , a specific example of the dye-coupling substance used therein is disclosed in JP-A-53-110,827.
No. 54-130. No. 927, No. 56-164,342, and No. 53-35,533.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. , No. 330,524, Japanese Patent Publication No. 48-39,165, and U.S. Patent No. 3,443,940, etc., diffusion is caused by the reaction between a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer. Substances that produce sex pigments are described in U.S. Pat. No. 3,227,550 and others.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
．． In order to improve this problem, we developed a method that does not require a developer.
Dye-releasing compounds that themselves have reducing properties have also been devised.

Representative examples are shown below along with literature. Definitions in the general formula are described in each literature.

U.S. Patent No. 4.055.428, etc. JP 59-69839 Bal 1st JP 53-3819, JP 51-104,343 JP 51-104,343 Bal last JP 51-1983 -104,343 Research Disclosure Magazine No. 17465 U.S. Patent No. 3.725.062 U.S. Patent No. 3,728,113 Ballist U.S. Patent No. 3,443,939 Various dye-donating substances mentioned above Any of these can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents cited above.

Diffusible dyes include those derived from azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine colors, and the like. The part may be temporarily converted to short wave.
For specific examples of dye moieties released from dye-donating compounds, see pages 37 to 59 of JP-A-59-84236.
Among them, the following are preferred.

Yellow dye (Dye-1) (Dye-2) (Dye-3) (Dye-4) Magenta dye (Dye-5) (Dye-6) (Dye-7) Cyan Dye (Dye-8) u (Dye-9) Dye-to (Dye-11) u In this invention, the dye-donating substance is disclosed in U.S. Patent No. 2,32
They can be introduced into the layers of the photosensitive material by known methods such as the method of No. 2,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 5.1-59
The polymer dispersion method described in No. 943 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the woody colloid, and these surfactants include those listed as surfactants elsewhere in this specification. can be used.

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

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Examples of the reducing substance include those generally known as reducing agents, as well as the above-mentioned dye-donating substances having reducing properties.

Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Image formation accelerators can be used in the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes;
It has functions such as promoting the movement of dyes from the light-sensitive material layer to the dye fixing layer, and from a physicochemical function, it has functions such as bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, silver or silver ions. It is classified as a compound that interacts with However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound may have multiple functions. many.

Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates as inorganic bases; Examples include ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc. Organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines)
; Aromatic amines (N-alkyl substituted aromatic amines,
N-hydroxylalkyl-substituted aromatic amines and bis(p-(dialkylamino)phenyltumethanes),
Examples include heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 8 or more are particularly preferred.

b Precursor base Precursors include salts of organic acids and bases that are decarboxylated and decomposed by heating, compounds that decompose and release amines by reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, Beckmann rearrangement, etc. Some kind of reaction occurs and the base is excised + sum^dai h4 ”k I / FR1
, 58-55.700, the 2-carboxycarboxamide derivatives described in U.S. Pat. No. 4,088,496, and the base component containing an alkali metal or alkaline earth metal in addition to an organic base. salts with thermally decomposable acids (Japanese Patent Application No. 58-69597), hydroxamic carbamates described in Japanese Patent Application No. 43860-1987 that utilize Rossen rearrangement, Japanese Patent Application No. 58-31 that produces nitriles by heating, Examples include fludoxime lupamates described in No. 614. Others: British Patent No. 998,945, U.S. Patent No. 3,220
．． No. 846, JP-A No. 50-22625, British Patent No. 2
, 079.480 and the like are also useful.

C- Water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols It is also possible to use salts or precursors of the above compounds.

A high boiling point organic solvent (so-called plasticizer) used as a solvent when emulsifying and dispersing a hydrophobic compound such as A) can be used.

Negative Q-natural L agent is solid at ambient temperature, melts near the development temperature and acts as a solvent, and is suitable for ureas, urethanes, amides, pyrudines, sulfonamides, sulfones, sulfoxides, and esters. , 40 for ketones and ether compounds
Those that are solid at temperatures below ℃ can be used.

■L Kai 1 亙ヱJ Pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, JP-A-59-57
Examples include polyalkylene oxides described in No. 231.

or ionic thiimides, nitrogen-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols, thioureas, and thioethers described in Japanese Patent Application No. 57-222247.

The image formation accelerator may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both. The layer to be incorporated may also be incorporated in the emulsion layer, intermediate layer, protective layer, dye fixing layer, and any layer adjacent thereto.
The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support.

The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Ugly precursors include, for example, oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305;
Compounds that release acids by Rossen rearrangement as described in Japanese Patent Application No. 59-85834 are included, and electrophilic compounds that undergo a substitution reaction with bases upon heating include, for example, Japanese Patent Application No. 59-858.
Examples include compounds described in No. 5836.

1・IL 77% Fll Jlh IA +I-*
II I↓ It is preferable to use it in the order of 1 - 1 - 1 - 1 because the effect is particularly exhibited.

In that case, the ratio (molar ratio) of base precursor/acid precursor is preferably 1/20 to 20/l, and 115 to 20/l.
5/1 is more preferred.

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time. Among them, inthiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in U.S. Patent No. 3,301,678, U.S. Patent No. 3,669,670
1,8-(3,6-thioxaoctane)bis(
Bis( intiuronium trichloroacetate) etc.
isothiuronium), West German Patent Publication No. 2,162,7
Thiol compounds described in No. 14, U.S. Pat. No. 4,012
, 2-amino-2-thiazolium trichloroacetate, 2-amino-5-bromoethyl-2 described in No. 260
- Thiazolium compounds such as thiazolium trichloroacetate, bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazolium phenylsulfonylacetate described in U.S. Pat. No. 4,060,420 Compounds having 2-carboxycarboxamide as an acidic moiety, such as, for example, are preferably used.

Furthermore, the 7-zole thioether and blocked azolinthione compounds described in Belgian Patent No. 768,071,
4-Aryl- as described in U.S. Pat. No. 3,893,859
1-Cal8mil-2-tetrazoline-5-thione compound, and other U.S. Patent Nos. 3,839,041 and 3,8
Compounds described in No. 44.788 and No. 3.877.940 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are 1.2.4-1-lyazole, IH-tetrazole, thiouracil and 1,
3.4-Thiadiazole and other compounds. Examples of preferred toning include 5-amino-1,3,4-f-diazole-2-thiol, 3-mercaph-1,2,
4-h lyazole, bis(dimethylcarbamyl) disulfide, 6-methylthiouracil, 1-phenyl-2-
Examples include tetraazoline-5-thione. Particularly effective toning agents are compounds capable of forming black images.

The concentration of the toning agent contained varies depending on the type of heat-developable photosensitive material, processing conditions, desired image, and other factors, but it is generally about o, oo to 1 mole of silver in the photosensitive material.
i~0.1 mole.

The binders used in the present invention can be contained alone or in combination.

A hydrophilic binder can be used for this binder. A typical example of the wood-loving binder is a transparent or translucent wood-loving binder.

The photographic light-sensitive materials and dye-fixing materials of the present invention may contain inorganic or organic hardeners in the photographic emulsion layer and other binder layers, such as 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-propatol, 1.2
-bis(vinylsulfonylacetamido)ethane, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-5-triazine, etc.), mucohalogen acids a, (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. As a general support,
Glass, paper, metal and their analogs are used, as well as cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related films or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. U.S. Pat. No. 3,634.

The polyesters described in No. 089 and No. 3.725.070 are preferably used.

In the present invention, when using a dye-donating substance that releases an image-wise mobile dye, it is preferable to use a transfer aid to transfer the dye from the photosensitive layer to the dye-fixing layer.
As the transfer aid, a dye transfer aid 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, or an inorganic alkali metal salt is used as the dye transfer aid. Also, methanol, N,N-dimethylformamide, acetone,
A low boiling point solvent such as diisobutyl ketone or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used.

The water used in the present invention is not limited to so-called "pure water", but includes water in the widely conventional sense.

Examples of water that can be used without invention include general drinking water and industrial water. For water used as general drinking water, for example, there are water quality standards for tap water in the United States and water quality standards set by the World Health Organization (WHO), and water that meets these standards corresponds to the water referred to in the present invention. do. Furthermore, water commonly used in various industries also corresponds to wood as referred to in the present invention. Water quality standards used in various industries can be found, for example, in the Sanitary Engineering Handbook, published by Asakura Shoten, 1967, 235.
6. , those that meet the criteria in E.
Whether it is ground water, river water, or to which chemicals have been intentionally added, such as alkalis such as caustic soda and caustic potash, vias, acids such as succinic acid, and metal salts such as zinc acetate, iron chloride, and calcium nitrate. , various water softeners, various antibacterial/heat protection agents, and various surfactants, such as the above-mentioned surfactants that can be used in the dye fixing layer, can be used as water in the present invention.

The amount of ice is sufficient as long as it is sufficiently thick to move the dye, but preferably it is 0.1 times the total weight of the dried coating film of the light-sensitive material and image-receiving material, or 0.1 times the total weight of the dry coated film of the light-sensitive material and image-receiving material. The amount can be used within the range obtained by subtracting the weight of the entire coating film from the weight of water corresponding to the maximum swelling volume.

The dye transfer aid may be used in a way that the dye transfer aid is wetted with the dye transfer aid.

If the transfer aid is incorporated into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside. - The transfer aid described in Section H 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, it is solid at room temperature. This is a method in which a photosensitive material or dye-fixing material incorporates a wood-philic thermal solvent that dissolves at high temperatures. The hydrophilic thermal solvent may be incorporated into either the light-sensitive material or the dye-fixing material, or may be incorporated into both.Also, the layers in which it is incorporated may include the emulsion layer, the intermediate layer, the storage layer, etc. It may be either the I layer or the dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

The above-mentioned wood-loving thermal solvent is a compound that is in a solid state at room temperature but turns into a liquid state when heated, and has an (inorganic/organic) value>1 and a water solubility at room temperature of 1 or more. Defined as a compound. Inorganicity and organicity are concepts used to predict the properties of compounds, and the details can be found in, for example, Chemistry, Vol. 1, p. 719 (1957).
It is described in. The wood-loving heat solvent is (inorganic/
It is an essential condition that the (organic) value is 1 or more, preferably 2 or more.

On the other hand, from the viewpoint of molecular size, it is considered preferable that molecules that can move by themselves without inhibiting the movement exist around the moving dye. Therefore, it is preferable that the molecular weight of the hydrophilic heat solvent is small, about 20
0 or less, more preferably about 100 or less.

It is sufficient that the wood-philic thermal solvent can substantially assist the movement of the wood-philic dye generated by the heating phenomenon to the dye-fixing layer, so it can not only be included in the dye-fixing layer, but also A wood-philic heat solvent can be contained in a photosensitive material such as a layer, 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, the hydrophilic thermal solvent is preferably contained in the dye fixing layer and/or its adjacent layer.

The wood-philic thermal solvent is usually dissolved in water and dispersed in the paint, but it can also be used by dissolving it in alcohols, such as methanol, ethanol, etc.

Examples of usable hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Specific examples of these hydrophilic heat solvents and particularly preferred examples include JP-A No. 58-420921
Examples include the compounds described on pages 149 to 158 of the issue.

These hydrophilic heat solvents can be used alone or
Two or more types can also be used together.

These hydrophilic thermal solvents are 10 to 300% by weight, preferably 20 to 200% by weight of the total coating film thickness excluding the woodphilic thermal solvent in the photosensitive material or dye fixing material. Particularly preferably, it can be used in a range of 30 to 150% by weight.

In the present invention, any of the two types of transfer aids can be used, but water and a wood-philic heat solvent are particularly preferred.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
1) if it contains a dye-donating substance represented by 1)
Since the dye-donating substance is colored, an anti-irradiation 1F substance, an anti-halation substance, or
Although it is not so necessary to incorporate various dyes into photosensitive materials, in order to improve the sharpness of images, they are disclosed in Japanese Patent Publication No. 48-3692 and U.S. Patent No. 3゜253.921.
No. 2.527,583, No. 2.956.87
It is possible to contain filter dyes, absorbent substances, etc., which are described in various specifications such as No. 9. These dyes are preferably thermally decolorizable, such as those described in U.S. Pat. No. 3,769.019 and U.S. Pat.
Dyes such as those described in No. 3,615,432 are preferred.

The photosensitive material used in the present invention may contain various additives known as developable photosensitive materials and layers 1 below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, and A.
It can contain an H layer, a release layer, etc. For various additives, see Research Disclosure Magazine v01゜1
70. Additives described in No. 17029 of June 1978, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, and matting agents.

Additives include surfactants, optical brighteners, and anti-fading agents.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide, and transparent or opaque thin films are made using known methods. be able to. In the latter method, conductive particles such as metal particles, carbon black, and graphite are dispersed in rubber, synthetic polymers, and gelatin to create a resistor with desired temperature characteristics. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat-generating element/support/photosensitive element support 7 Heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating element support/photosensitive element/intermediate layer 7 After exposure to heat-generating element or after exposure The heating temperature in the heat development step in a substantially water-free state can be approximately 0°C to approximately 250°C, but particularly useful is approximately 110°C to approximately 180°C. Within this range, the temperature is preferably 140°C or higher, particularly 15°C.
The heating temperature in the transfer step is preferably 0° C. or higher, and transfer can be performed in the range from the temperature in the heat development step to room temperature, but it is more preferably about 1θ° C. lower than the temperature in the heat development step. Development and Alternatively, as a heating means in the transfer process, a simple hot plate, iron, hot roller, heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. Alternatively, a dye transfer aid may be applied to both, and then the two may be superimposed.

Examples of methods for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include the roller coating method or wire bar coating method as described in Japanese Patent Application Laid-open No. 58-55907, and the method described in Japanese Patent Application No. 58-55908. A method of applying wood to a dye-fixing material using a water-absorbing member as described, and a method of applying a bead between a heat-developable photosensitive material and a dye-fixing material as described in Japanese Patent Application No. 58-55906. Method for applying dye transfer aid by forming, Japanese Patent Application No. 58-5591
As described in No. 0, a method of forming beads between a water-repellent roller and a dye fixing layer to apply a dye transfer aid, other methods include a deep method, an extrusion method,
Various methods can be used, such as a method in which the material is applied by jetting it out from pores, a method in which the material is applied by crushing a bod, and the like.

The dye transfer aid may be measured in advance and given in an amount within the range as described in Japanese Patent Application No. 58-37902, or
The amount can be adjusted and used by applying sufficient amount and then squeezing it out by applying pressure with a roller or the like or drying it by applying heat.

For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing between pressurized rollers, and then the material is superimposed on a photothermographic material.

The heating means in the transfer process includes heating by passing between hot plates or heating by contacting with the hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635).
(No. 43-10791), heating by contacting a heated drum or heated roller while rotating (for example, Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, Japanese Patent Publication No. 53-3273)
No. 7), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source using a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. can be used. . In addition, graphite, carbon black,
Layers of electrically conductive material, such as metal, may be applied and the electrical current may be passed through the electrically conductive layers to heat them directly.

The heating temperature applied in the transfer process is within the range from the temperature in the thermal development process to room temperature, but in particular,
The temperature is preferably 0° C. or more and 10° C. or more lower than the temperature in the heat development step.

The pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact varies depending on the embodiment and the materials used.
0.1~100kg/c■2 Preferably 1~50kg
/ cm2 is appropriate (for example, Japanese Patent Application No. 58-5569
(described in No. 1).

Various methods can be used to apply pressure to the photothermographic material and the dye-fixing material, such as passing it between a pair of rollers or pressing it using a plate with good smoothness. Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

V. Specific Effects of the Invention According to the present invention, the diffusible dye distributed in an image is diffused under high temperature conditions, and the layer that fixes the diffused dye and/or the layer adjacent thereto contains an ultraviolet absorber. As a result, a dye-fixing material that has excellent light fastness and provides color images with less light stain can be obtained.

① Specific Examples of the Invention One specific example of the present invention will be shown below, and the effects of the present invention will be explained in more detail.

Example 1 The following first layer (lowest layer) to sixth layer (top layer) were coated on a polyethylene terephthalate film support to prepare a color photosensitive material having a multilayer structure.

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

28 g of gelatin and 13.2 g of benzotriazole were made into 3000 mM of water. 40% of the solution
The mixture was kept at ℃ and stirred. Add 17g of silver nitrate to this solution and 10g of water.
A solution dissolved in 0 mJL was added over 2 minutes. The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30, and a yield of 400 g of benzotriazole silver emulsion was obtained.

The method of making the silver chlorobromide emulsion used in the first and fifth layers will be described.

A well-stirred gelatin aqueous solution (gelatin 20 g and sodium chloride 3 in 100 100 O of water)
600 m of an aqueous solution containing sodium chloride and potassium bromide (containing 600 m of water and kept at 75°C) and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 m of water) were simultaneously heated for 40 minutes. Added at flow rate.

In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 uLm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-
Chemical sensitization was carried out at 60° C. by adding 20 mg of hydroxy-6-methyl-1,3°3a,7-chitrazaindene. The yield of emulsion was 600 g.

The method of making the silver halide emulsion used in the third layer will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 10,100 O of water)
600 mjL of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 mM of water) were simultaneously added at equal flow rates over a period of 40 minutes. did.

In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 9.35 g, m was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-
Chemical sensitization was carried out at 60° C. by adding 20 mg of hydroxy-6-methyl-1,3°3a,7-chitrazaindene. The yield of emulsion was 600 g.

This article describes how to make a gelatin dispersion of a dye-donating substance.

Weighed 5 g of the yellow dye-donating substance (A) shown below, 0.5 g of sodium succinate 2-dithylhexyl ester sulfonate as a surfactant, and 30ml of ethyl was added and dissolved by heating to about 60°C to form a homogeneous solution. After stirring and mixing this solution and a long lO% solution of lime-treated gelatin, the mixture was heated at 10.000'r for 10 minutes using a homogenizer.
Dispersed at pm. This dispersion is called a yellow dye-providing substance dispersion.

Magenta dye-donating substance (B) as a dye-donating substance
A dispersion of a magenta dye-providing substance was prepared in the same manner as above except that 7.5 g of tricresyl phosphate was used as the high boiling point solvent.

A dispersion of a cyan dye-providing substance was prepared in the same manner as the yellow dye dispersion except that a cyan dye-providing substance (C) shown below was used as the dye-providing substance.

Dye-donating substance (A) 4]'' Dye-donating substance (C) Coagulation υ Q The color photosensitive material with the above multilayer structure uses a tungsten bulb, and G, R, and IR three whose density changes continuously Color separation filter (G: 500-600 nm, R: 600-600 nm
700 nm bandpass filter, IR is 700
(constructed using a filter that transmits at least 5 nm)
Exposure was performed for 1 second at 00 lux.

Thereafter, it was heated uniformly for 20 seconds on a heat block heated to 150°C.

Next, we will describe how to make a dye-fixing material that can receive images.

First, gelatin hardener H-10.75g, H-20.2
5g and 155mJL of water and 1% surfactant W-1
5 mjL and 10% lime-processed gelatin i00 g were mixed uniformly.

This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to form a wet film of 60 pm, and then dried.

Gelatin hardener H-1 CH2TomiCHSO2CH2C0NH-CH2CH2NH
COCH2-502CH=CH2 gelatin hardener H-
2 CH2ECH3O2CH2C0NHCH2・CH2CH
2N HCOCH2S 02 CH=H2 Surfactant w-i Next, 15 g of a polymer with the following structure and 5 g of polyvinylpyrrolidone (degree of polymerization 3000) were dissolved in 180 ml of water, and treated with 5% surfactant W-32mi and lθ% lime. 100 g of gelatin was mixed uniformly. This mixed solution was uniformly applied onto the above-mentioned coating material to form a wet film of 85 μm.

polymer Surfactant W-2 Shii3 Surfactant W-3 The above coating layer is used as a dye fixing layer.

To this dye fixing layer, the following ultraviolet absorbers dissolved in tricresyl phosphate and dispersed in lime-treated gelatin were added so that the ultraviolet absorber concentration was 300 mg/m', and the dye was dried. Fixed materials 101-104
I got it. In addition, a dye fixing material 201 containing no ultraviolet absorber was also produced in the same manner.

Dye fixing material Ultraviolet absorber 201 None A tungsten bulb was used in the multilayered color photosensitive material, and a G, R1IR three-color separation filter with continuously changing density (G was 500 to 600 nm, R was 600 to 600 nm)
700nm bandpass filter, ZR is 700nm
(constructed using a transmission filter).

Exposure was performed for 1 second at 500 lux.

It was heated uniformly for 30 seconds on a heat block heated to 44140°C.

Next, after supplying 20 ml of water per 1 ml to the film side of each of the dye fixing materials listed in h. Superimposed. After heating on a heat block at 80°C for 6 seconds, the dye fixing material is peeled off from the light-sensitive material, and yellow, magenta, and cyan colors are deposited on the fixing material, corresponding to the G and RlIR three-color separation filters, respectively. A color image was obtained.

Next, these dye-fixing materials with negative images are processed using Atlas C.
, I65 weatherometer was used, and the color image was irradiated with canon light (100,000 lux) for 3 days. Macbeth's reflection densitometer (RD) was used to measure the color image density before and after irradiation with senone light.
-519), and the fastness of the color image to light was evaluated by determining the dye residual rate.

Incidentally, the dye residual rate was determined according to the following formula.

Dye residual rate (%) In addition, using the same measurement method as above, the amount of change in minimum density (Δ
DB) and evaluated STEIN.

ΔDB=DB (after light irradiation) - DB (before light irradiation) These results are shown in Table 1.

Table 1 shows that the uninvented dye fixing material has a high dye residual rate and a small change in minimum density.

Therefore, the effects of the present invention are obvious.

Further, on the dye fixing layer of the dye fixing material 201 that does not contain the ultraviolet absorber, the ultraviolet absorber (11),
(20), (6) and (28), respectively, dissolved in tricresyl phosphate and dispersed in lime-treated gelatin, coated with an ultraviolet absorber of 300 mg/m'', and dried. A similar effect was obtained using .

Example 2 Using the multilayered color photosensitive material used in Example 1,
The dye fixing material described below was prepared without using water during transfer, and the same evaluation as in Example 1 was performed.

We will describe how to make dye-fixing materials.

Dissolve 12g of lime-treated gelatin in 200mJL of water,
To this was added 16 ml of a 0.5M zinc acetate aqueous solution and mixed uniformly. This mixed solution was uniformly applied to a 1100B white film support made of polyethylene terephthalate containing titanium dioxide to a wet film thickness of 85Bm. Next, prepare the following coating solution on top of this.

A dye-fixing material was prepared by uniformly applying a wet film thickness of 90 pm and drying.

(Dye fixing layer coating solution formulation) Polyvinyl alcohol (degree of polymerization 2000) 10% aqueous solution 120g Urea
20g N-methylurea 20g water
60m
The following UV absorbers were dissolved in tricresyl phosphate and dispersed in lime-treated gelatin, and then added to the dye fixing layer so that the UV absorber was 300 mg/rn' and dried to produce one color J. Fixed materials 301-304
I got it. Further, the dye fixing material containing no ultraviolet absorber was designated as 401.

Dye fixing material Ultraviolet absorber 401 None In the color photosensitive material of the multilayer structure of Example 1, a tungsten bulb was used to continuously change the density of G, R,
It was exposed to 500 lux for 1 second through an IR three-color separation filter. Thereafter, the mixture was heated uniformly for 30 seconds using L-deblock-h heated to 140°C.

This photosensitive material was layered with the previously prepared dye fixing material so that the film surfaces were in contact with each other, passed through a pressurized heat roller at 130°C, and then immediately heated to 30°C on a heat block.
Heated for 0 seconds. Immediately after heating, the dye-fixing material was peeled off from the light-sensitive material, and yellow, magenta, and cyan color images corresponding to the G and RlIR three-color separation filters were obtained on the dye-fixing material, respectively.

The dye residual rate stain was evaluated in the same manner as in Example 1.

These results are shown in Table 2.

From Table 2, it can be seen that the dye fixing material of the present invention has a high dye residual rate and a small change in minimum density.

Therefore, the effects of the present invention are obvious.

Procedural amendment button January 28, 1986 1, Indication of case, 1982 Patent Application No. 258779 2, Name of invention Dye fixing material 3, Person making amendment Relationship with case Patent applicant Address Kanagawa Prefecture Minamiashigara City Nakabō 210##Place name
Name (520) Fuji Photo Film Co., Ltd. 4, Agent 101 'II 864-4498 Address No. 6, 3-2, Iwamoto-cho, Chiyoda-ku, Tokyo Contents of amendment (1) Line 9, page 17 of the specification "Polyvinylpyroton" in the eyes
is corrected to "polyvinylpyrrolidone".

(2) Correct "color mixture" on page 26, line 6 of the same page to "fading".

(3) "Proteins such as gelatin derivatives, polyvinyl alcohol, cellulose derivatives, etc." on page 26, lines 12 to 14 will be corrected to "proteins such as gelatin derivatives, cellulose derivatives."

(4) "Belongs" in line 13 of page 30 of the same page is "belongs"
and correct it.

(5) Replace pages 39 to 41 as shown in the attached sheet.

(6) "High-boiling organic solvents such as those listed below" in the fourth to third lines from the bottom of page 46 are corrected to "high-boiling organic solvents."

(7) "Pirudines" on page 51, line 14 is corrected to "pyridines."

(8) "2-carboxycarboxamide" on page 55, line 5 is corrected to "α-sulfonylacetate."

(9) From the 1st line from the bottom of page 66 to the 2nd line of page 67, “A temperature of about 10°C to about 180°C is useful, and this...
"preferably 150°C or higher" is replaced with "about 110°C to about 180°C"
°C is useful. ” he corrected.

(10) In the second line of page 70, “use embodiment” is changed to “
Embodiment, use” is corrected.

(11) Replace page 81 as shown in the attached sheet.

(12) Delete "The above-mentioned multilayer structure was heated to..." from lines 1 to 9 on page 83.

JP-A-51-104,343 JP-A-51-104,343 Research Disclosure Magazine 17465 US Patent No. 3,725,062 US Patent No. 3,728,113 Ba1list US Patent No. 3. Any of the various dye-providing substances described in No. 443.939 above can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents listed above.

Claims (1)

[Claims] Diffusible dyes distributed in an image form are diffused under high temperature conditions,
A dye fixing material having a layer for fixing a diffusing dye, characterized in that the fixing layer and/or an adjacent layer contain an ultraviolet absorber.