JPH11149145A - Dyestuff fixing element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dyestuff fixing element small in tendency to yellow in the circumference of the dyestuff fixing element in the case of storing the dyestuff fixing element before and after output of an image for a long period. SOLUTION: The dyestuff fixing element contains a mordant and a base and/or a base precursor on one side of a support and a gelatin in an amount of >=10 weight % and a polymer having cationic functional groups in an amount of >=10 weight % in a barrier layer on the other side of the support. The coating amount of the barrier layer is 0.1-1.0 g/m<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a dye fixing element used in an image forming method of a dye diffusion transfer system. Furthermore, the present invention relates to a dye-fixing element having improved coloring at the periphery of an image when stored for a long period of time.

[0002]

2. Description of the Related Art A dye fixing element used for a dye diffusion transfer type image forming material generally contains a mordant, and a method of forming an image by fixing a dye to be diffused and transferred to the mordant by ionic interaction. Is used. The dye fixing method according to this method is not limited to the dye that is transferred by diffusion,
Ionic substances present in the air and water-soluble ionic substances also have the drawback of mordanting, fixing and coloring.

As such mordant and coloring substances, vanillin, 2,6-di-tert-butyl paranitrophenol (hereinafter abbreviated as BNP) and the like are known. Especially BN
P originates from 2,6-di-tert-butyl paramethylphenol (also known as 2,6-di-tert-butylhydroxytoluene, abbreviated as BHT hereinafter), which is very commonly added as an antioxidant in the production of various polymer materials. As a result of oxidation and nitration. For this reason, BNP is generally present in the atmosphere, and when the dye-fixing element is stored for a long period of time, it mordants to the dye-fixing element and develops a yellow color.

[0004] This yellowing due to BNP has no practical prevention method other than blocking BNP from the image receiving layer because BNP is generally present in the atmosphere and the mordant has no selective mordant ability. One way to achieve this is
A method of providing a layer having a barrier property with respect to a substance represented by mordant-colored BNP which is present in the atmosphere is disclosed in Japanese Patent Application No. Hei 8 (1996) -197686.
-123511. One of the materials having a barrier property is gelatin. When a barrier layer containing gelatin is formed, it is preferable to dispose it on the side opposite to the image receiving layer. This is because, when the barrier layer containing gelatin is provided on the same surface as the image receiving layer, the diffusible substance in the image receiving layer diffuses into the barrier layer and significantly damages the barrier layer, and the barrier layer is provided on the opposite side of the image receiving layer. This is because the application amount must be increased as compared with the case. However, when a barrier layer containing gelatin is provided on the opposite side of the image receiving layer, for example, when two sheets are stacked in the same direction, in a state where the image receiving layer and the barrier layer are in contact with each other,
It was found that the base and / or the base precursor in the image receiving layer migrated to the barrier layer side and had a significant effect on image formation. In such diffusion of the base and / or the base precursor, the larger the coating amount of the barrier layer, the larger the diffusion amount, and the greater the effect on image formation. In order to solve this problem, it has been desired to develop a barrier layer that can effectively suppress mordanting of an ionic substance other than a dye with a small coating amount.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dye-fixing element in which the dye-fixing element hardly yellows when the dye-fixing element is stored for a long time before and / or after image output. Therefore, the barrier layer to be installed is made thinner.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye-fixing element containing a mordant and a base and / or a base precursor on one side of a support; A barrier layer containing at least 10% by weight of a polymer compound having a cationic functional group, and the coating amount of the barrier layer is 0.1 to 1.
Achieved by a dye-fixing element characterized by 0 g / m ² .

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the barrier layer, on one surface of the support,
This is a layer having a barrier property against a compound represented by BNP, which is a substance causing a phenomenon in which a dye-fixing element containing a mordant and a base and / or a base precursor turns yellow during long-term storage. In the present invention, the “layer having a barrier property against BNP” refers to a layer in which the dye fixing element has a different yellowing speed due to BNP depending on whether or not the layer is present, and is described in Japanese Patent Application No. 8-123511. By conducting a yellowing compulsory test and comparing the degree of yellowing, the presence or absence of barrier properties can be confirmed.

As the polymer compound having a cationic functional group, a polymer containing a monomer unit having a quaternary ammonium salt for at least one month or more is preferable, and a polymer compound represented by the general formula [1] is particularly preferable. . General formula [1]-(A) _p- (B) _{q- wherein} A represents at least one vinyl monomer unit having a quaternary ammonium salt. B represents at least one vinyl monomer unit having no quaternary ammonium salt. The sum of p is 2 to 100%, and the sum of q is 0 to 98%.

The vinyl monomer unit (A) in the general formula [1] of the present invention is preferably specifically represented by the general formula [2]. General formula [2]

[0010]

Embedded image

In the formula, R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. L represents a divalent linking group having 1 to 20 carbon atoms. n is 0 or 1
Represents R ₂ , R ₃ and R ₄ are the same or different 1
An alkyl group having ~ 12 carbon atoms, or 7 ~
Represents an aralkyl group having 20 carbon atoms, R ₁ ,
R ₂ , R ₃ and R ₄ may be mutually connected to form a cyclic structure. Y ^- is a monovalent anion.

In the present invention, the content of gelatin in the barrier layer is 10% by weight or more, and the content of the high molecular compound having a cationic functional group in the barrier layer is 10% by weight or more. The content of gelatin in the layer is 30% by weight or more, and the content of the high molecular compound having a cationic functional group which forms the barrier layer is 10% by weight or more.

The coating amount of the barrier layer is from 0.1 g / m ^{2 to} 1.0 g / m ^2.
g / m ^2, preferably from 0.1 to 0.5 g / m ^2. This is that if the coating amount is small, the barrier property is reduced, if too large, the curling is deteriorated, and in a state where the image receiving layer and the barrier layer are in contact with each other,
This is because there is a possibility of causing an adverse effect such that the diffusible substance moves to the barrier layer side in the image receiving layer.

The coating position of these barrier layers is desirably provided on the side opposite to the image receiving layer with respect to the support. This is because the barrier layer to be installed is separated by the support from the vicinity of the image receiving layer where diffusion transfer occurs, so that it does not inhibit the diffusion transfer of the dye, and is affected by other polymers and inorganic salts in the image receiving layer. This is because the barrier is reduced.

There are no particular restrictions on the coating method and form of each material, but simultaneous coating when manufacturing a support or when manufacturing an image receiving film is effective in reducing the manufacturing time and cost. It is also effective to form a barrier layer after applying a prepolymer to increase the molecular weight.

The barrier layer may be mixed with other materials of the above-mentioned components. Particularly, aldehyde hardener, aziridine hardener, epoxy hardener, vinyl sulfone hardener, N-methylol hardener, etc. 17, 643, page 26; 18,7
No. 16, page 651, left column. 307, 105, 874
Addition of a known photographic hardener described on pages 875 to 875 improves the film properties and is effective.

The photothermographic material used in the present invention basically has a photosensitive silver halide and a binder on a support, and further comprises, if necessary, an organic metal salt oxidizing agent.
A dye-donating compound (which may also serve as a reducing agent as described later) and the like can be contained.

These components are often added to the same layer, but they can be added separately in separate layers if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, JP-A-59-180550, JP-A-64-13546, 62-
253159, European Patent Publication No. 479,167, and the like, a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer;
There are a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer, a combination of a red-sensitive layer, an infrared-sensitive layer (I), and an infrared-sensitive layer (II). Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary as described in JP-A-1-252954.

In the photothermographic material, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layers and as the lowermost layer. An auxiliary layer may be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, a layer structure as described in the above patent, an undercoat layer as described in U.S. Pat. No. 5,051,335, a solid pigment as described in JP-A-1-1677838 and JP-A-61-20943. Intermediate layer having
Nos. 53, 5-34884 and 2-64634, an intermediate layer having a reducing agent and a DIR compound, U.S. Pat. Nos. 5,017,454 and 5,139,919;
An intermediate layer having an electron transfer agent as described in JP-A-2-235444, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer obtained by combining them can be provided.

When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer has an antistatic function and a surface resistivity of 10 ¹² Ω · cm.
It is preferable that the design is made as follows.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed.
As described in JP-A-167743 and JP-A-4-223463, a method of mixing monodispersed emulsions and adjusting the gradation is preferably used. The particle size is 0.1-2 μm, especially 0.2-
1.5 μm is preferred. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,
No. 029 (1978), No. 17, 643 (December 1978)
Nos. 22-23, ibid. 18,716 (November 1979), 648
Page, No. 307, 105 (November 1989) pp. 863-865,
JP-A-62-253159, JP-A-64-13546,
JP-A-2-236546 and JP-A-3-110555 and "Physics and Chemistry of Photography" by Grafkid, published by P. Glafkides, Chemie et Phisique Photographiqu
e, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, published by Focal Press (GF Duffin, Photograp)
hic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zerikman et al., Published by Focal Press (VL Zelikman et al., Making and Coating).
Any of silver halide emulsions prepared by the method described in Photographic Emulsion, Focal Press, 1964) can be used.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to perform so-called desalting for removing excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and 5-1
Emulsions described in JP-A-81246 and the like are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B No. 47-1
Organic thioether derivatives described in 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Gla
fkides, Chemie et Phisique Photographique, Paul Mo
ntel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion)
Chemistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikman et al., Published by Focal Press (VL
Zelikman et al., Making and Coating Photographic E
mulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used.

An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can be used. Further, in order to accelerate the grain growth, the addition concentration, amount and rate of silver salt and halogen salt to be added may be increased (Japanese Patent Application Laid-Open No. 55-142).
Nos. 329 and 55-158124; U.S. Pat.
No. 50, 757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set as desired depending on the purpose. The preferred pH range is between 2.2 and 7.0, more preferably between 2.5 and 6.0.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type photosensitive material, A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-110555).
No. 5-241267). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-40446
Can be used. PH during chemical sensitization
Is preferably 5.3 to 10.5, more preferably 5.5.
To 8.5, and the pAg is preferably 6.0 to 10.
5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
617,257, JP-A-59-180550, 6
4-135546, JP-A-5-45828, 5-4
Sensitizing dyes described in US Pat. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization and adjusting the wavelength of spectral sensitivity.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. Patent Nos. 3,615,641 and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a process and the known photographic additives that can be used in the present invention are described in the above-mentioned RD.
No. 17, 643; 18,716 and N
o. 307 and 105, and the corresponding portions are summarized in the following table.

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Brightener page 24 page 648 right column page 868 5. 5. Fogging prevention page 24-25 page 649 right column 868-870 page Agents, stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filters-page 650, left column, dyes, ultraviolet absorbers 7. Dye image area page 25 page 650 left column page 872 stabilizing agent 8. Hardening agent page 26 page 651 left column 874-875 Binder page 26 page 651 left column pages 873 to 874 10. Plasticizer, page 27, page 650, right column, page 876, lubricant 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 12. 12. Static 27 pages 650 right column 876-877 Inhibitors Matting agent 878-879

As the binder for the constituent layers of the photosensitive material and the dye fixing element, hydrophilic binders are preferably used. Examples thereof include those described in the aforementioned Research Disclosure and pages (71) to (75) of JP-A-64-13546. Specifically, a transparent or translucent hydrophilic binder is preferable. For example, proteins such as gelatin and gelatin derivatives, other animal proteins (eg, egg white, egg yolk, casein, whey protein, etc.) or cellulose derivatives, starch, Arabic Natural compounds such as rubber, dextran, polysaccharides such as pullulan and polyvinyl alcohol,
Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. In particular, polyvinyl alcohol or a copolymer of vinyl alcohol and a vinyl monomer having a carboxylic acid group and those whose terminals are alkyl-modified are preferably used for the purpose of improving the stability of dispersions such as emulsions and latexes. U.S. Pat. No. 4,960,681;
Or a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymer of the vinyl monomers or with another vinyl monomer (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin in which the content of calcium and the like is reduced according to various purposes. Is also preferred. It is also possible to constitute a binder free of so-called gelatin which does not use any gelatin.

When a system for performing thermal development by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. When a polysaccharide is used for the dye-fixing layer or its protective layer as described in JP-A-7-36163 or the like, the dye is transferred from the dye-fixing element to another one after transfer. Transfer can be prevented. In the present invention, the coating amount of the binder is 1 m ^2.
It is preferably 20 g or less, more preferably 10 g or less, and even more preferably 7 g or less.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 10 g / m ² .
1 to 4 g / m ² are suitable.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. Nos. 4,500,626, columns 49-50, 4,839,272, 4,330,617, 4,590,152, 5,017,454, and 5; 139, 919, JP-A-60-140335, pp. (17) to (18), pp. 57-40245, pp. 56-13.
Nos. 8736, 59-178458 and 59-538
No. 31, No. 59-182449, No. 59-18245
No. 0, No. 60-119555, No. 60-128436
No. 60-128439, No. 60-198540
No. 60-181742, No. 61-259253
No. 62-244444 and No. 62-131253
Nos. 62-131256 and 64-13546, pages (40)-(57), JP-A-1-120553, and EP-A-220,746A2, pages 78-96. And reducing agent precursors. U.S. Pat. No. 3,039,
Combinations of various reducing agents, such as those disclosed in US Pat. No. 869, may also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, in order to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. Particularly preferably, said US Patent No. 5,139,
No. 919 and European Patent Publication No. 418,743 are used. Also, JP-A-2-230143 and JP-A-2-230143.
A method of stably introducing the compound into the layer as described in JP-A-235044 is preferably used.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3.
-Pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols, JP-A-53-110827, U.S. Pat. Nos. 5,032,487 and 5,026,634
And the compounds described as electron donors in JP-A-4,839,272 and dye-donating compounds having diffusion resistance and reducing property described later. In addition, Japanese Patent Laid-Open No. 3-1
An electron donor precursor as described in JP-A-60443 is also preferably used.

Further, the above-mentioned reducing agent can be used in the intermediate layer or the protective layer for various purposes such as prevention of color mixing and improvement of color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,040, JP-A-4-249245, and 2-
No. 46450 and JP-A-63-186240 are preferably used. In addition, Japanese Patent Publication 3-63733
No., JP-A-1-150135, JP-A-2-46450,
Development inhibitor releasing reducing compounds as described in JP-A-2-64634, JP-A-3-43735, and EP-A-451,833 may also be used. In the present invention, the total amount of the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

In the present invention, silver can be used as an image forming substance. In addition, when silver ions are reduced to silver under high temperature conditions, they may contain a compound that generates or releases a mobile dye corresponding to this reaction or vice versa, that is, contains a dye-donating compound. it can.

Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Examples of color developers and couplers are TH Jame
s "The Theory of the Photogrtaphic Process", 4th edition, pages 291-334 and 354-361, RD No. 307, 1
No. 05, page 871, JP-A-58-123533, and JP-A-58-123533.
No. 149046, No. 58-149047, No. 59-
No. 111148, No. 59-124399, No. 59-1
No. 74835, No. 59-231539, No. 59-23
No. 1540, No. 60-2950, No. 60-2951
Nos. 60-14242, 60-23474 and 60-66249.

As another example of the dye donating compound,
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI]. ((Dye) _m -Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image A difference in the diffusivity of the compound represented by ((Dye) _m -Y) _n -Z corresponding to or opposite to a photosensitive silver salt having a latent image, or (Dye) _m
-Y, and released (Dye) _m -Y and ((Dy
e) _m- Y) _n- Z represents a group having a property that causes a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, m, n Are not 1, both Dyes may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. In the following,-is to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "is" to form a diffusible dye image (positive dye image) in response to the development of silver halide. (A negative dye image).

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972, and JP-B-3-68387. And a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in US Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. . Examples thereof include compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and isoxazolone described in US Pat. No. 4,199,354. Compounds that release a diffusible dye by an intramolecular ring rewinding reaction are included.

US Pat. No. 4,559,290, EP 220,746 A2, US Pat. No. 4,783,
No. 396, published technical report 87-6, 199, Japanese Unexamined Patent Publication No. 64-1
As described in JP-A No. 3546, JP-A-6-301181 and the like, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used.

For example, see US Pat. No. 4,139,
No. 389, No. 4,139,379, JP-A-59-18.
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. Nos. 4,232,107
No., JP-A-59-101649, and JP-A-61-88257.
No. 24,025 (1984) and the like, which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A
JP-A-56-142530, U.S. Pat.
Nos. 3,893 and 4,619,884, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, and are described in U.S. Pat. No. 4,450,223. Examples include nitro compounds that release a diffusible dye after electron acceptance, and compounds described in US Pat. No. 4,609,610 that release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220,746A2, published technical report 87-6,199,
U.S. Pat. No. 4,783,396, JP-A-63-201
No. 653, No. 63-201654, No. 64-1354
No. 6, etc., in one molecule, an NX bond (X is oxygen,
Sulfur or a nitrogen atom) with a compound having an electron-withdrawing group, the compound SO ₂ -X (X has the same meaning as defined above) and an electron attractive group in one molecule described in JP-A-1-26842, A compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271344, and a compound having an electron-withdrawing group in one molecule described in JP-A-63-271341 C—X ′ bond (X ′ is the same as X or
SO ₂ —) and a compound having an electron-withdrawing group. Also, JP-A-1-161237 and JP-A-1-16
No. 1342, compounds capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used. Among them, especially NX in one molecule
Compounds having a bond and an electron withdrawing group are preferred.

Compounds having a diffusible dye as a leaving group and releasing a diffusible dye by reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940 and 4,474,867
No. 4,483,914 and the like.

A compound (DRR compound) that is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312 and 4,053,312,
Nos. 4,055,428 and 4,336,322, JP-A-59-65839, JP-A-59-69839, and JP-A-5-6939
No. 3-3819, No. 51-104343, RD NO.1
No. 7,465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-11637, JP-A-57-179840, and JP-A-6-301179. No. 6,301,180 and U.S. Pat. No. 4,500,626. Among them, the compounds described in U.S. Pat. No. 4,500,626 in columns 22 to 44 and the compounds described in U.S. Pat. No. 4,639,408 in columns 37 to 39 are useful. Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure, May 1978, pages 54 to 58, etc.). Azo dyes (US Pat. No. 4,235,957, Research Disclosure, April 1976, pp. 30-32, etc.) and leuco dyes (US Pat. No. 3,985) , 565,4,022,6
No. 17) and a non-diffusible dye donating compound having a heterocyclic ring containing a nitrogen atom, a sulfur atom or a selenium atom (JP-A-59-180548).

Hydrophobic additives such as a dye-donating compound and a diffusion-resistant reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
470, 4,536,466, 4,536,4
Nos. 67, 4,587,206 and 4,555,47
No. 6,4,599,296, JP-A-63-3064
No. 39, No. 62-8145, No. 62-30247,
A high-boiling organic solvent as described in JP-B-3-62256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g per 1 g of the dye-providing compound used.
g. In addition, 1 cc or less per gram of binder,
Further, 0.5 cc or less, particularly 0.3 cc or less is appropriate.

JP-B-51-39853, JP-A-51-39853
A dispersion method using a polymer described in No. 59943 can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, those described as the surfactants described in Research Disclosure, pages 37-38 of JP-A-59-157636, can be used. Further, a so-called polymer dispersant can also be used. Also, Japanese Patent Laid-Open No. 7-5
No. 6,267, 228589 and West German Patent Application No. 1,932,299A can also be used.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of dyes, various dyes and colored matters are fixed or made colorless in the constituent layers of the light-sensitive material of the present invention to improve the white background of the obtained image. Compounds can be added. Specifically, compounds described in EP-A-353,741, EP-A-461,416, JP-A-63-163,345 and JP-A-203,158 can be used.

Various pigments and dyes can be used in the constituent layers of the light-sensitive material of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure, and EP-A-479,167.
No. 502,508, JP-A-1-1677838,
Compounds described in JP-A-1-343355, JP-A-2-168252, JP-A-61-20943, JP-A-6-337511 and the like can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photosensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing element used in the present invention has at least one layer containing a mordant. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
-88256, pages (32) to (41) and JP-A No. 1-16123
No. 6, pages (4) to (7), mordants described in JP-A-62-244.
Nos. 043 and 62-244036. No. 4,463,073.
A dye-receiving polymer compound as described in No. 9 may be used. The binder used in the dye fixing element of the present invention is preferably the above-mentioned hydrophilic binder. Further, it is preferable to use carrageenans and polysaccharides such as dextran as described in EP-A-443,529 in combination.

Auxiliary layers such as a protective layer, a release layer, and an anti-curl layer can be provided on the dye fixing element, if necessary. It is particularly useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a high boiling organic solvent can be used as a plasticizer, a slipping agent, an anti-curl agent or an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective. JP-A-62-215953 and JP-A-63-464.
The silicone oil described in No. 49 is also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), and JP-A-54-48535, 62-13
Nos. 6641 and 61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
JP-A Nos. 62-174741 and 61-88256 (1)
7) to (29), JP-A-63-199248, JP-A-1-75
568, 1-74272 and the like.

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or supplied to the dye-fixing element from outside such as a light-sensitive material. You may. For the same purpose, as described in JP-A-6-118592, two or more kinds of polymers may coexist in the mordant layer to control the balance of hydrophilicity / hydrophobicity and the polarity of the presence site of the microscopic dye. It is valid. As a combination of polymers to be phase-separated, for example, gelatin and dextran, PVA and gelatin, polyimidazole and polyacrylic acids, PEG and gelatin are effective. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., “The Chemis
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agent, ultraviolet absorber and fluorescent whitening agent are described in JP-A-62-215272.
Nos. (125) to (137), JP-A-1-161236 (17) to (4)
It is described on page 3).

The hardeners used in the constituent layers of the light-sensitive material and the dye-fixing element include the aforementioned Research Disclosure,
U.S. Pat. No. 4,678,739, column 41, 4,795;
1,042, JP-A-59-116655, and 62-
Nos. 245261 and 61-18942, JP-A-4-24-2
No. 18044 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g, per 1 g of gelatin applied.
5 to 0.5 g are used. The layer to be added may be any of the layers constituting the light-sensitive material and the dye-fixing element.
It may be added in layers or more. In the absence of gelatin, 0.001 per g of the polymer compound reacted with the hardener
1-1 g is used.

Various antifoggants or photographic stabilizers and precursors thereof can be used in the constituent layers of the light-sensitive material and the dye-fixing element. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627 and 4,614,702, and JP-A-64-13546 (7).
To (9), (57) to (71) and (81) to (97), U.S. Patent Nos. 4,775,610, 4,626,500, 4,983,494, JP-A-62-174747,
62-239148, JP-A-1-150135,
No. 2-110557, No. 2-178650, RDN
o. 17, 643 (1978) (24) to (25) and the like. These compounds are available in 5 moles per mole of silver.
X 10 ^-6 to 1 x 10 ^-1 mol is preferred, and 1 x 10
^-5 to 1 × 10 ^-2 mol is preferably used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants may be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, accelerating development, and stabilizing a dispersion. Can be. Specific examples of surfactants can be found in the research
Disclosure, JP-A Nos. 62-173463 and 62-183457. For the purpose of stabilizing the dispersion, an oligomer type polymer surfactant is preferably used.

The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of the organic fluoro compound include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

A matting agent can be used for the light-sensitive material and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952. In addition, the compounds described in the aforementioned Research Disclosure can be used.

In addition, the constituent layers of the light-sensitive material and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pp. (26)-(32);
No. 11338 and Japanese Patent Publication No. 2-51496.

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. A specific example is described in U.S. Pat.
Nos. 4,493, 4,657,848 and the like. In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing element from the viewpoint of improving the storage stability of the photosensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a combination of a compound (hereinafter referred to as a complex-forming compound) capable of forming a complex with a metal ion constituting the hardly-soluble metal compound, Compounds that generate a base by electrolysis described in JP-A-61-232451 can also be used as the base precursor. In particular, the former method is effective. This poorly soluble metal compound and complex forming compound
It is advantageous to add them separately to the light-sensitive material and the dye-fixing element.

In the present invention, various development terminators can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development by interacting with a compound or silver and silver salt to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, a support capable of withstanding the processing temperature is used as a support for the light-sensitive material and the dye-fixing element. In general, The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", Corona Co., Ltd. (1979)
Photographic supports such as paper and synthetic polymers (films) described on pages (223) to (240). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further, Film-processed synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, Ceramic or the like is used. These can be used alone, or a support laminated on one or both sides with a synthetic polymer such as polyethylene, PET, polyester, or polystyrene can be used.

In addition, JP-A-62-253159 (2)
9) to (31), JP-A-1-161236 (14) to (17),
JP-A-63-316848, JP-A-2-22651
No. 3-56955, U.S. Pat. No. 5,001,03
The support described in No. 3 or the like can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports. It is also preferable to coat a polymer such as gelatin or PVA on the surface of the support in advance for the purpose of improving the wettability of the coating solution and the adhesion between the coated film and the support.

The thickness of the support varies depending on the purpose of use, but is usually 40 μm or more and 400 μm or less. However, in the case of a method in which an image is formed using an element applied on two or more separate supports, the non-image-side support on the element ultimately has a thinner support than the aforementioned range. A body (5 μm or more and 250 μm or less) is preferably used. As such a thin support, for example, PET
A film on which aluminum is deposited is used.
Particularly when heat resistance and curl characteristics are strictly required, JP-A-6-41281 and JP-A-6-43 are used as supports for photosensitive materials.
No. 581, No. 6-51426, No. 6-51437,
Nos. 6-51442, 6-82961, 6-82
No. 960, No. 6-123937, No. 6-107646
Nos. 6-67346, 6-118561, 6
-266050, 6-202277, 6-17
No. 5282, No. 6-118561, No. 7-21912
9, the support described in 7-219144 can be preferably used.

As a method of exposing and recording an image on a photosensitive material, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers via an electric signal, a method of exposing image information to a CRT, a liquid crystal display, There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc., JP-A-2-53378.
And the light source and the exposure method described in JP-A-2-54672 can be used. Further, a light source using a blue light emitting diode, which has been remarkably developed recently, and a green light emitting diode in combination with a red light emitting diode can be used. Especially,
Japanese Patent Application Nos. 6-40164, 6-40012, 6
No. 42732, No. 6-86919, No. 6-86920
Nos. 6-93421, 6-94820 and 6-948
Exposure apparatuses described in Nos. 96628 and 6-149609 can be preferably used.

Further, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KD).
P), inorganic compounds such as lithium iodate, BaB ₂ O ₄ , and urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM) -Oxide derivatives, JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTS).
A television signal represented by C), an image signal obtained by dividing an original image into a number of pixels such as a scanner, and an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive material and / or dye-fixing element of the present invention can be used for various purposes. For example, the dye fixing element after the heat development transfer can be used as a positive or negative color print material. Also, by using a photosensitive material using a black dye-donating substance or a mixture of yellow, magenta, and cyan dye-donating substances, a printing material such as a black-and-white positive-type or negative-type printing material or a lithographic material. Alternatively, it can be used as a radiographic material. In particular, when used as a material for printing from photographic materials, JP-A-6-163450 and 4-33.
Using imaging materials with information recording capability as in 8944,
It is preferred that the photosensitive material of the present invention is exposed to light and developed and transferred to form a print on the dye fixing element of the present invention. As this printing method, Japanese Patent Application Laid-Open No.
-19364 and 5-19363 can be used.

The photosensitive material after the heat development transfer can be used as a photographic material by appropriately desilvering. In that case, as a support, for example, JP-A-4-124
No. 645, No. 5-40321, No. 6-35092,
It is preferable to record photographing information and the like using a support having a magnetic layer described in JP-A-6-318457.

The light-sensitive material and / or dye-fixing element of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is described in JP-A-61-14554.
No. 4, etc. can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and especially about 60 ° C.
180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is particularly preferably at least 50 ° C. and about 10 ° C. lower than the temperature in the heat development step.

Although the movement of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably from 50C to 100C.

Examples of the solvent used for accelerating the development and / or for diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image forming accelerator The low-boiling solvent or a mixed solution of the low-boiling solvent and water or the above-mentioned basic aqueous solution can be used. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent.

Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer. As the water, any water can be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the thermal developing apparatus using the photosensitive material and the image receiving element of the present invention, water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144354 and JP-A-63-14
Nos. 4355 and 62-38460, JP-A-3-210
No. 555 or the like or water may be used.

These solvents can be applied to the light-sensitive material, the dye-fixing element or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. Examples of the method for applying water include, for example, JP-A No. 62-253159, page (5) and JP-A No. 63-8
The method described in No. 5544 is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive material or the dye-fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied is 30 ° C. as described in JP-A-63-85544.
The temperature may be up to 60 ° C.

In order to promote dye transfer, a system in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the light-sensitive material and / or the dye-fixing element may be employed. The layer to be incorporated may be any of a light-sensitive silver halide layer, an intermediate layer, a protective layer and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oxyls, and other heterocycles.

As a heating method in the developing and / or transferring step, a heated block or a plate is brought into contact, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater, an infrared and far infrared lamp heater are used. For example, or by passing through a high-temperature atmosphere. A method of superposing a light-sensitive material and a dye-fixing element is described in JP-A-62-253159 and JP-A-6-253159.
The method described in 1-1147244, page 27, can be applied. Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-177754, JP-A-59-181353, and JP-A-69-17835.
No. 0-18951, Japanese Utility Model Application Laid-Open No. 62-25944, Japanese Patent Application Nos. 4-277517, 4-2433072, 4-2.
No. 44693, No. 6-164421, No. 6-1644
An apparatus described in No. 22 or the like is preferably used. Commercially available devices include a Pictrostat 100, a Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd.
Pictrostat 300, Pictography 30
00 and Pictography 2000 can be used.

[0090]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Nothing was applied to the high-density polyethylene side of the polyethylene laminated paper having the structure shown in Table 1, and the surface coating having the structure shown in Table 2 was applied to the low-density polyethylene side to produce an image forming material D101. This image forming material is an image receiving layer having no layer having a barrier property to BNP.

Further, a layer having the contents shown in Table 3 was applied to the high-density polyethylene side of the polyethylene laminated paper having the structure shown in Table 1, and a surface coating having the structure shown in Table 2 was applied to the low-density polyethylene side to obtain an image forming material D109. ~ D114 was created. These six types of image forming materials are image receiving materials having a layer having a barrier property against BNP on the side opposite to the image receiving layer with respect to the support.

Further, a layer having the contents shown in Table 3 was applied to the high-density polyethylene side of the polyethylene laminated paper having the structure shown in Table 1, and a surface coating having the structure shown in Table 2 was applied to the low-density polyethylene side to obtain an image forming material D102. To D108. These seven types of image forming materials are image receiving materials having a polymer material constituting the barrier layer of D109 to D114 alone on the side opposite to the image receiving layer with respect to the support.

These 14 types of image receiving materials generate a base by being bonded to a photosensitive material together with a small amount of water, and are fixed by mordanting dyes released and diffused from the photosensitive material as a result of thermal development. It has the ability.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

1. Forced coexistence test with BNP The image forming materials, D101 to D114, were placed on a glass plate with the mordant-coated surface facing down, and the periphery was fixed with cellophane tape. Glass plate with image forming material attached
After sealing in a closed container with P powder, keep at 40 ° C for 1
Left for a week. Thereafter, the yellow density of the mordant-coated surface is
-Measured with a RITE 310 densitometer. Table 3 shows the results.

2. Evaluation of yellowing due to natural aging D101 to D114 were cut into A4 size, overlapped so that the mordant applied surface faced a certain direction, closed in an office file, and left for one year under natural aging. Thereafter, it was evaluated whether yellowing was observed in the surrounding area. This result is also shown in Table 3.
Are shown together.

[0104]

[Table 3]

From these results, it was found that by coating a barrier layer containing gelatin and a polymer having a cationic functional group, it was possible to obtain a longer coating amount with a smaller coating amount than when each was coated alone. It can be seen that yellowing around the image during storage can be prevented.

[0106]

According to the dye-fixing element of the present invention, yellowing of the peripheral portion of an image can be satisfactorily prevented even after long-term storage.

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[Procedure amendment]

[Submission date] January 21, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] As the polymer compound having a cationic functional group is preferably a polymer containing a monomer unit having on at least Ke than the quaternary ammonium salts, polymer compounds represented by the Among these general formulas (1) preferable. General formula [1]-(A) _p- (B) _{q- wherein} A represents at least one vinyl monomer unit having a quaternary ammonium salt. B represents at least one vinyl monomer unit having no quaternary ammonium salt. The sum of p is 2 to 100%, and the sum of q is 0 to 98%.

Claims (1)

[Claims] 1. A dye-fixing element comprising a mordant and a base and / or a base precursor on one side of a support, and gelatin on the other side containing 10% by weight or more of gelatin.
And a barrier layer containing a polymer compound having a cationic functional group in an amount of 10% by weight or more, and the coating amount of the barrier layer is 0.1 to 1.0 g / m ^2. element.