JPH04355752A - Dye fixing element - Google Patents

Abstract

PURPOSE:To obtain a transferred dye image free from silver stains by incorporating an organic compound capable of forming silver salt having a solubility product of <=10<-13> in the water of PH10 in the dye fixing element. CONSTITUTION:An image is formed by forming a photosensitive element containing at least photosensitive silver halide, a reducing agent and/or its precursor, and a dye donor, imagewise diffusing and transferring a dye from this element, and fixing it. At that time, the organic compound capable of forming the silver salt having a solubility product of <=10<-13> in the water of PH10 is contained in the dye fixing element, and this organic compound is optionally selected so long as it satisfies the above mentioned requirement, and preferably, the compound represented by formula I in which Ro is an aliphatic, aromatic, or hetero-cyclic group; S in a sulfur atom: and M is an alkali metal atom.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye-fixing material that diffusely transfers and fixes dyes from a photosensitive element containing photosensitive silver halide.

0002

[Prior Art] Photography using silver halide has been the most widely used method since 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. However, in the photographic method using silver halide, an image of reduced silver and a color image are generated simultaneously during development, and therefore, there is a drawback that the color image becomes cloudy.

[0003] In order to improve these drawbacks, a mobile (diffusible) dye is formed or released in an image form during development, and this mobile dye is fixed with a mordant using a solvent such as water or a hot solvent. Many methods of transferring to elements have been proposed.

[0004] In this method of forming an image by transferring a mobile dye, some means (for example, heat, high pH, pressure, ultrasonic waves, electromagnetic waves, etc.) is used to promote the diffusion transfer of the dye. . At this time, it was found that the diffusivity of compounds having diffusivity other than the dye was also increased, resulting in the formation of silver (Ag°) stain on the dye fixing element.

This phenomenon is caused by the fact that when a mobile dye is formed or released, a part of the silver halide in the photosensitive element forms a diffusible complex with a silver-soluble compound, and the silver ion complex is transferred to the dye-fixing element. This is thought to occur because silver diffuses into the atmosphere and is reduced to silver (Ag°) by some action there. Furthermore, when the reducing agent or reducing agent precursor is incorporated into the photosensitive element, its effect is remarkable.

Therefore, it is necessary to prevent such silver staining, and Japanese Patent Application Laid-open No. 163345/1983 proposes a method of incorporating a silver ion scavenger into a photosensitive element. However, the inclusion of silver ion scavengers in photosensitive elements often presents great difficulties in maintaining photographic properties. Therefore, it has been desired to prevent the above-mentioned silver stain without impairing photographic properties.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dye-fixing element free of the above-mentioned silver stains without impairing photographic properties.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to imagewise transfer a dye from a photosensitive element containing on a support at least a photosensitive silver halide, a reducing agent and/or a reducing agent precursor, and a dye-providing compound. A dye fixing element for an image forming method that involves diffusion transfer and fixation, characterized in that the dye fixing element contains an organic compound capable of forming a silver salt having a solubility product in water of pH 10 of 10-13 or less. This problem was solved by a dye-fixing element.

The present invention will be explained in detail below. The organic compound that can form the poorly soluble silver salt used in the present invention may be any organic compound as long as the solubility product of the silver salt in water at pH 10 is 10-13 or less, but preferred structures include the following general structures. Mention may be made of compounds of formula (A). General formula (A) R0-S-M In the formula, R0 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group, and each of these substituents is 1
It may further have the above substituents. S represents a sulfur atom. M represents a hydrogen atom or an alkali metal atom.

Among the compounds of general formula (A), more preferred compounds are those represented by general formula (B) or general formula (C). General formula (B)

[0011]

[Chemical formula 1]

In the formula, R11 represents an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group or an aryl group, and each of these substituents may further have one or more substituents. Examples of substituents contained in R11 include alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkoxycarbonyl groups, amino groups, and N-substituted amino groups. , acylamino group, carbamoyl group, N-substituted carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, N-substituted sulfamoyl group, cyano group, hydroxyl group, nitro group, These include halogen atoms. Among these, preferred substituents are an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a sulfonylamino group, and a halogen atom. l represents an integer from 0 to 5, and R11 may be the same or different when l is 2 or more. General formula (C)

[0013]

[Case 2]

In the above general formula (C), Q is an oxygen atom, a sulfur atom, or a -N(R')- group (R' is a hydrogen atom, an alkyl group, an unsaturated alkyl group, or a substituted or unsubstituted aryl group, respectively). or an aralkyl group), Y and G are each a carbon atom or a nitrogen atom, R12 and R13 are each a hydrogen atom, an alkyl group,
It represents an unsaturated alkyl group, a substituted or unsubstituted aryl group or aralkyl group, -SR'' or -NH2 (R'' group is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkylcarboxylic acid or an alkali metal salt thereof, or a group of alkylsulfonic acid or its alkali metal salt), when both Y and G are carbon atoms, R
12 and R13 may form a substituted or unsubstituted aromatic carbocycle or nitrogen-containing heterocycle. Among the compounds of general formula (C), particularly preferred compounds are the following general formulas (C-1), (
It is a compound represented by C-2) or (C-3).

[0015]

[Chemical formula 3]

Preferred specific examples of the compounds represented by the general formulas (A), (B), and (C) are shown below, but the invention is not limited thereto.

[0017]

[C4]

[0018]

[C5]

[0019]

[C6]

[0020]

[C7]

[0021]

[Chemical formula 8]

[0022]

[Chemical formula 9]

[0023]

[Chemical formula 10]

[0024]

[Chemical formula 11]

[0025]

[Chemical formula 12]

[0026]

[Chemical formula 13]

[0027]

[Chemical formula 14]

[0028]

[Chemical formula 15]

[0029]

[Chemical formula 16]

[0030]

[Chemical formula 17]

[0031]

[Chemical formula 18]

[0032]

[Chemical formula 19]

[0033]

[C20]

As a modification of the compound represented by the general formula (A), a polymeric antifoggant having a repeating unit represented by the following general formula (D) as one of the substituents of R0 is also useful. General formula (D)

[0035]

[C21]

Here, R21 represents a hydrogen atom or a lower alkyl group having up to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, hexyl group). Especially preferred as R21 are a hydrogen atom and a methyl group. Although L is a divalent linking group, it is preferable that the total number of carbon atoms is 1 to 20. Among such linking groups, those represented by the following formula (L-I) or (L-II) are particularly preferred. (L-I) -CO-Q-(Z)m'-(Y)n'-(L-II)

[0037]

[C22]

In the formula, Q is -O- or -N(R22)-
(Here, R22 represents a hydrogen atom or a lower alkyl group. The lower alkyl group preferably has up to 6 carbon atoms.) Z is an alkylene group (preferably one with up to 10 carbon atoms. An amide bond, ester bond, or ether bond may be interposed between the alkylene groups. For example, a methylene group, an ethylene group, a trimethylene group,
2-hydroxytrimethylene group, -CH2OCH2-,
-CH2CONHCH2-, etc.), or arylene group (
Preferably one having 6 to 12 carbon atoms. For example, p-phenylene group, etc.), and Y represents -COO-, -OCO-,
-CONH-, -NHCO-, -SO2NH-, -NH
Represents SO2- etc. Also, m' and n' are each 0 or 1
represents an integer. Preferred divalent linking groups as L include, for example, the following.

[0039]

[C23]

[0040]

[C24]

Other examples of L will be listed below.

[0042]

[C25]

A polymeric antifoggant having a repeating unit represented by the general formula (D) generally has the following general formula (E).
It can be obtained by polymerizing the unsaturated monomer represented by either alone or by copolymerizing it with an ethylenically unsaturated monomer copolymerizable with this monomer.

[0044]

[C26]

Specific examples of the unsaturated monomer represented by the general formula (E) are shown below, but the compounds of the present invention are not limited thereto.

[0046]

[C27]

[0047]

[C28]

[0048]

[C29]

[0049]

[C30]

The polymeric antifoggant used in the present invention may be one obtained by polymerizing monomer units of the general formula (E) as described above, or an ethylenically unsaturated one that can be copolymerized with the monomer of the general formula (E). It may also be a copolymer with one or more monomers. Preferred ethylenically unsaturated monomers in this case include those listed above as copolymerizable monomers for the polymeric complex-forming compound. Among these ethylenically unsaturated monomers, monoethylenically unsaturated esters of aliphatic acids or their saponified products, sodium 2-acrylamido-2-methylpropanesulfonate, N
- vinylpyrrolidone, esters of ethylenically unsaturated monocarboxylic acids (e.g. hydroxyethyl acrylate, hydroxyethyl methacrylate), amides of ethylenically unsaturated monocarboxylic acids (e.g. acrylamide, methacrylamide), vinylbenzenesulfonic acids Salt etc. are preferred.

Homopolymerization of the monomer represented by general formula (E) and copolymerization with other ethylenically unsaturated monomers are as follows:
For example, Biochemistry page 1535 (19
Ronald L., described in 1975). Sch
nar, YuanChuan Lee et al., Journal of Polymer
Science; Polymer Chemistry
y Edition 2155 pages (1976)
Antony Winston, G.
lenn r. The method of McLaughlin et al.
Die Makromolekule Chemi
Hans-Georg Batz, Johanna, vol. 177, p. 683 (1976).
The method of Koldehott et al., Angewante
Chemie; International. Edit. 1
Hans-G described on page 103 (1972)
eorg Batz, Giselner Fran
zmann, Helmut Rings dorf
The method of P. et al., Polymer, p. 462 (1972). Ferruti, A. Bettel
This can be carried out by the method of li, Angelino Fere, etc.

[0052] The degree of polymerization of the polymeric antifoggant can be arbitrarily selected. Although it is not easy to accurately determine their molecular weight, the average molecular weight determined by a light scattering method or GPC method is preferably in the range of approximately 5×10 3 to 3×10 6 . When using a copolymer with an ethylenically unsaturated monomer, the copolymerization ratio can be arbitrarily selected, but at least the molar percentage of the repeating unit represented by the general formula (D) is 0.1 It is preferable that the amount of the copolymer is at least 1 mol %, particularly at least 1 mol %. Specific examples of the polymer antifoggants used in the present invention are shown below.

[0053]

[Chemical formula 31]

[0054]

[C32]

Antifoggant precursors that can be used for the purposes of the present invention include compounds capable of releasing the abovementioned antifoggants by thermal, alkaline or redox reactions. For example, JP-A No. 61-67849, JP-A-61-67849;
-124941, 61-147244, 61-
No. 269147, No. 61-185744, Patent Application No. 1983
-221569, 61-88625, and the like. Among these, those that uniformly release the antifoggant regardless of the image are preferred. Specifically, there are the following compounds.

[0056]

[Chemical formula 33]

[0057]

[C34]

[0058]

[C35]

The antifoggant or antifoggant precursor used in the present invention usually contains -S- per equivalent of total coated silver.
It can be used in the range of 10-5 to 10-1 equivalent in terms of the functional group represented by M, but preferably 10-4 to 10-2
Equivalent range. When a hydrophobic antifoggant or an antifoggant breaker is dissolved in an organic solvent that is immiscible with water, it can be dissolved in the organic solvent, emulsified and dispersed, and then added. It may be added as a fine particle dispersion prepared by the method described in No. 53-102733. When using a water-soluble binder, the above-mentioned polymer antifoggant used in the present invention can be added as an aqueous solution by selecting a water-soluble polymer compound, or can be added as a water-soluble polymer compound in an organic solvent that is immiscible with water. It is also possible to add a molecular compound by dissolving it in the organic solvent and emulsifying and dispersing it. Moreover, it can also be dispersed and added in the form of latex. When it is contained in a hydrophobic binder, it can be added after being dissolved in an organic solvent that dissolves the binder. In the present invention, the layer to which the silver ion scavenger is added can be any layer in the photosensitive material, such as a photosensitive layer, an intermediate layer, or a protective layer, but the layer closest to the dye fixing element is particularly preferred.

The dye-fixing element of the present invention forms or releases a diffusible dye as a result of development of the silver halide in a photographic material using photosensitive silver halide, and transfers this diffusible dye to an image-receiving material. It is used as an image-receiving material in a method to obtain images. This image forming method can be roughly divided into the so-called wet color diffusion transfer method, which develops using a processing liquid at around room temperature, and the heat development diffusion transfer method, which develops by heat development. It can also be used as a suitable image receiving material. Since the dye fixing element of the present invention is particularly preferably used in a heat development diffusion transfer system, it will be explained in detail below. , can be applied in common with the wet color diffusion transfer method.

The heat-developable photosensitive material used in the present invention basically has a photosensitive silver halide and a binder on a support, and if necessary, an organometallic salt oxidizing agent,
A dye-donating compound (which may also serve as a reducing agent as described later) can be contained. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. Although the reducing agent is preferably incorporated into the photothermographic material, it may also be supplied from the outside by, for example, diffusing it from a dye fixing element described below.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination. . For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials. Further, each of these photosensitive layers may be divided into two or more layers as necessary. The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

The silver halide that 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 and a photofog. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. The particle size is preferably 0.1 to 2 μm, particularly 0.2 to 1.5 μm. The crystal habits of silver halide grains are cubic, octahedral,
It may be a tetradecahedron, a flat plate with a high aspect ratio, or any other shape. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, selenium sensitization methods, etc. for emulsions for conventional light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-Open No. 62-25315
No. 9). 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 the present invention, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the organic silver salt oxidizing agents described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 626, columns 52-53. Also, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 13235, and
Acetylene silver described in No. 249,044 is also useful. Two or more types of organic silver salts may be used in combination. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m 2 in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include azoles and azaindenes described in RD17643 (1978) pages 24-25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. The 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.
No. 60-140335, RD17029 (197
Examples include the sensitizing dyes described on pages 12 and 13 of 8th year). These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. ，
No. 615,641, JP-A No. 63-23145, etc.). These sensitizing dyes may be added to the emulsion during or before chemical ripening, or as described in U.S. Pat.
, 183,756 and 4,225,666 before or after nucleation of silver halide grains. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

Hydrophilic binders are preferably used for the constituent layers of the photographic material and the dye fixing element. Examples include pages (26) to (2) of JP-A-62-253159.
Examples include those listed on page 8). Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and pullulan, and polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, super absorbent polymers described in JP-A No. 62-245260, etc.
That is, homopolymers of vinyl monomers having -COOM or -SO3M (M is a hydrogen atom or an alkali metal), or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g., sodium methacrylate,
Ammonium methacrylate, Sumikagel L-5H (manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders are 2
It is also possible to use a combination of two or more species.

[0069] When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to rapidly absorb water. Furthermore, when a highly water-absorbing polymer is used in the dye-fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye-fixing element to another object after transfer. In the present invention, the amount of binder applied is preferably 20 g or less per m2, particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or dye-fixing element contain additives for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitization and desensitization. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A-62-245258, JP-A-62-136648, JP-A-62-110066, etc. can be used. especially,
Using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent the mordant layer from cracking, and using a polymer latex with a high glass transition point for the back layer can prevent curling. .

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used. Examples of reducing agents used in the present invention include U.S. Pat. No. 4,500,626;
Columns 9 to 50, Columns 30 to 31 of No. 4,483,914, No. 4,330,617, No. 4,590,152,
JP-A No. 60-140335, pages (17) to (18), No. 57-40245, No. 56-138736, No. 59-178458, No. 59-53831, No. 59
-182449, 59-182450, 60-
No. 119555, No. 60-128436 to No. 60-
Up to No. 128439, No. 60-198540, No. 60
-181742, 61-259253, 62-
No. 244044, No. 62-131253 to No. 62-
There are reducing agents and reducing agent precursors described in pages 78 to 96 of European Patent No. 220,746A2. Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

When using a diffusion-resistant reducing agent, an electron transfer agent and/or an electron transfer agent may be added as necessary 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. The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below. In the present invention, the amount of reducing agent added is 0.00% per mole of silver.
01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, silver can be used as the image forming substance. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. can. Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a polymer chain. Specific examples of color developers and couplers are given by T. H. Jam
“The Theory of the
Photographic Process” No. 4
Edition pages 291-334 and 354-361, Japanese Patent Application Publication No. 1973.
No. 8-123533, No. 58-149046, No. 58
-149047, 59-111148, 59-
No. 124399, No. 59-174835, No. 59-2
No. 31539, No. 59-231540, No. 60-29
No. 50, No. 60-2951, No. 60-14242,
It is described in detail in No. 60-23474, No. 60-66249, etc.

[0074] Further, as another example of the dye-providing compound,
Compounds that have the function of releasing or diffusing a diffusible dye in an imagewise manner can be mentioned. This type of compound can be represented by the following general formula [LI]. (Dye-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 a linking group, and Z represents a latent image in an image-wise manner. (Dy
e-Y) Create a difference in the diffusivity of the compound represented by n-Z, or release Dye, and the released Dye
and (Dye-Y)n-Z, n represents 1 or 2, and when n is 2, two Dye-Ys are the same. But they can be different. Specific examples of the dye-providing compound represented by the general formula [LI] include the following compounds (1) to (2). In addition, ■ to ■ below correspond inversely to the development of silver halide to form a diffusive dye image (positive dye image), and ■ and ■ correspond to the development of silver halide to form a diffusible dye image. It forms a dye image (negative dye image).

■US Patent No. 3,134,764, No. 3
, No. 362,819, No. 3,597,200, No. 3,
544,545, 3,482,972, etc., a dye developer in which a hydroquinone developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. ■As described in US Pat. No. 4,503,137, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used. Examples include compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions described in U.S. Patent No. 3,980,479, and isoxazolone described in U.S. Pat. No. 4,199,354. Examples include compounds that release diffusible dyes through intramolecular rewinding reactions of rings.

■US Patent No. 4,559,290, European Patent No. 220,746A2, US Patent No. 4,783,
As described in No. 396, Kokai Technical Report 87-6199, etc., non-diffusible compounds that release diffusible dyes by reacting with the reducing agent remaining unoxidized during development can also be used. Examples include U.S. Patent No. 4,139,389, U.S. Pat.
No. 57-84453, etc., a compound that releases a diffusible dye by an intramolecular nucleophilic substitution reaction after being reduced, U.S. Patent No. 4,232,107, JP-A-59
-101649, 61-88257, RD240
25 (1984) etc., a compound which releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3,008,588A, JP-A-1988-1
42530, U.S. Patent No. 4,343,893, U.S. Pat.
, 619,884, etc., which releases a diffusive dye by cleavage of a single bond after reduction, and a compound that releases a diffusible dye after accepting electrons, as described in U.S. Pat. No. 4,450,223, etc. Nitro Compounds that Release, U.S. Patent No. 4,
Examples include compounds that release a diffusible dye after accepting electrons, as described in No. 609,610 and the like.

[0077]More preferably, European Patent No. 220,746A2, Published Technical Report No. 87-6199, US Pat.
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in No. 53, No. 63-201654, etc., JP-A-1-2684
Compound having SO2-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 2, JP-A-63-27
1344, a compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A No. 6
Examples include compounds having a C-X' bond (X' is synonymous with X or represents -SO2-) and an electron-withdrawing group in one molecule as described in No. 3-271341. Also, JP-A-1-
Compounds described in No. 161237 and No. 1-161342 that release a diffusible dye by cleavage of a single bond by a π bond conjugated with an electron-accepting group after reduction can also be used. Among these, compounds having an N-X bond and an electron-withdrawing group in one molecule are particularly preferred. A specific example is European Patent No. 22
No. 0,746A2 or U.S. Pat. No. 4,783,396
Compounds (1) to (3), (7) to (10) described in No.
), (12), (13), (15), (23) to (26
), (31), (32), (35), (36), (40
), (41), (44), (53) to (59), (64
), (70), and compounds (11) to (23) described in Kokai Technical Report 87-6199.

(2) A compound having a diffusible dye as a leaving group and which releases the diffusible dye upon reaction with an oxidized form of a reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, U.S. Pat.
No. 4,483,914, etc. ■A compound (D
RR compound). Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent. A typical example is U.S. Patent Nos. 3 and 9.
No. 28,312, No. 4053,312, No. 4,055
, No. 428, No. 4,336,322, JP-A-59-6
No. 5839, No. 59-69839, No. 53-3819
No. 51-104343, RD17465, U.S. Patent No. 3,725,062, U.S. Patent No. 3,728,113, U.S. Pat.
No. 57-179840, U.S. Patent No. 4,500,
It is described in No. 626, etc. Specific examples of DRR compounds include the aforementioned U.S. Pat. No. 4,500,626, No. 22.
Compounds described in columns to column 44 can be mentioned,
Among them, compounds (1) to (3) described in the above US patent,
(10) - (13), (16) - (19), (28) -
(30), (33) to (35), (38) to (40),
(42) to (64) are preferred. Also, U.S. Patent Nos. 4 and 6
Also useful are the compounds described in No. 39,408, columns 37-39. In addition, couplers mentioned above and general formula [LI]
Other dye-donating compounds include dye silver compounds that combine organic silver salts with dyes (Research Disclosure Magazine 1).
May 1978 issue, pages 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Pat. No. 4,235,95, etc.)
No. 7, Research Disclosure Magazine, 1976.4
year, pages 30-32, etc.), leuco dyes (U.S. Patent No. 3,
No. 985,565, No. 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-providing compounds and diffusion-resistant reducing agents can be introduced into the layers of the light-sensitive material by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454,
59-178455, 59-178457, etc., as necessary.
It can be used in combination with a low boiling point organic solvent of 0°C to 160°C. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing compound used. Further, it is appropriate that the amount is 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less per 1 g of binder. Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59943
The dispersion method using polymers described in No. In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above. When dispersing hydrophobic compounds into hydrophilic colloids,
A variety of surfactants can be used. For example, those listed as surfactants on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Pat. No. 4,500,62.
No. 6, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye fixing element is used along with the light-sensitive material. The dye fixing element may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat.
No. 00,626, columns 58-59 and JP-A-61-8825
The mordant described in No. 6, pages (32) to (41), JP-A-6
Examples include those described in No. 2-244043 and No. 62-244036. Also, U.S. Patent Nos. 4 and 4
Dye-receiving polymeric compounds such as those described in US Pat. No. 63,079 may also be used. The dye fixing element can be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

[0081] 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 slippery agent, or a peelability improving agent between the light-sensitive material and the dye-fixing element. A specific example is JP-A No. 62-253159 (25
), No. 62-245253, etc. Furthermore, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used for the above purpose. Examples include various modified silicone oils, especially carboxy-modified silicone (trade name: X-
22-3710) etc. are effective. Also, JP-A-62-
Silicone oils described in No. 215953 and No. 63-46449 are also effective.

[0082] Antifading agents may be used in the light-sensitive materials and dye fixing elements. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes. Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (such as U.S. Patent No. 3,533,794), 4-thiazolidone compounds (such as U.S. Patent No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective. Examples of metal complexes include U.S. Pat. No. 4,241,155, U.S. Pat. No. 61-88256 (2
7)-(29) pages, No. 63-199248, JP-A-1
There are compounds described in No.-75568, No. 1-74272, etc.

[0083] Examples of useful anti-fading agents are disclosed in JP-A-62-21
No. 5272, pages (125) to (137). The 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 may be supplied to the dye-fixing element from outside the photosensitive material. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination. A fluorescent brightener may be used in the light-sensitive material or 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 the light-sensitive material. An example is K. Edited by Veenkataraman “The
Chemistry of Synthetic
Dyes” Volume V Chapter 8, JP-A-61-143752
Examples include compounds described in No. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds. Optical brighteners can be used in combination with antifade agents.

As the hardening agent used in the constituent layers of the light-sensitive material and dye fixing element, US Pat. No. 4,678,739 No. 4 is used.
Column 1, JP-A-59-116655, JP-A No. 62-2452
61, No. 61-18942, and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinylsulfone hardeners (N,N'-ethylene-
bis(vinylsulfonylacetamido)ethane, etc.), N
-Methylol hardeners (dimethylol urea, etc.) or polymer hardeners (compounds described in JP-A-62-234157, etc.).

Various surfactants can be used in the constituent layers of the light-sensitive material and the dye fixing element for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like. Specific examples of surfactants are JP-A-62-173463;
It is described in No. 62-183457 and the like. 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 electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17, and Japanese Patent Publication No. 61-2094.
4, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. can be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described in No. 1-88256 (page 29), JP-A-63-274944, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 63-274952. others,
The constituent layers of the light-sensitive material and the dye fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A No. 61-8825.
No. 6, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye fixing element. 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 diffusible dyes, and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and silver. It is also classified as a compound that interacts with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40. Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. A specific example is U.S. Patent No. 4,511,493.
No. 62-65038, etc.

In a system in which thermal development and dye transfer 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 in order to improve the storage stability of the photosensitive material. In addition to the above, European Patent Publication No. 210,660, U.S. Patent No. 4,740,445
Combinations of poorly soluble metal compounds and compounds that can form complexes with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds), as described in JP-A No. 1986-
Compounds that generate bases by electrolysis as described in No. 232451 can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye fixing element separately.

In the present invention, various development stoppers can be used in the light-sensitive material and/or dye-fixing element in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development. The development stopper mentioned 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 their precursors. For more details, see JP-A-62-25
No. 3159, pages (31) and (32).

In the present invention, as a support for the light-sensitive material or dye fixing element, one that can withstand processing temperatures is used. Generally, paper, synthetic polymer (film)
can be mentioned. Specifically, films made of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), or films containing pigments such as titanium oxide, as well as polypropylene, etc. film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (
In particular, materials such as cast coated paper), metal, cloth, glass, etc. are used. These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition to this,
The supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods for exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, etc. A method of scanning and exposing an original image through a slit using an exposure device of a copying machine, a method of transmitting image information to a light emitting diode, various lasers, etc. via an electric signal, and a method of transmitting image information to a CRT, liquid crystal display, etc. There is a method of outputting the image to an image display device such as an electroluminescence display or a plasma display and exposing it directly or via an optical system.

[0092] As a light source for recording an image on a photosensitive material,
As mentioned above, U.S. Patent No. 4 for natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc.
, 500, 626, column 56 can be used. Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as BaB2O4, urea derivatives, nitroaniline derivatives, such as 3-
Methyl-4-nitropyridine-N-oxide (POM)
Nitropyridine-N-oxide derivatives such as and compounds described in JP-A-61-53462 and JP-A-62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful. The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. It is possible to use image signals created using a computer, such as signals, CG, and CAD.

The photosensitive material and/or the dye fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye. In this case, the transparent or opaque heating element is
Those described in No. 45544 etc. can be used. The conductive layer also functions as an antistatic layer. The heating temperature in the heat development step can be developed at about 50°C to about 250°C, and particularly useful is about 80°C to about 180°C. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 50° C. or higher and up to about 10° C. lower than the temperature in the heat development step.

[0094] Dye migration can also be caused by heat alone, but
A solvent may be used to facilitate dye transfer. Also,
As detailed in JP-A-59-218443 and JP-A-61-238056, it is also useful to carry out development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (especially water). be. In this method, the heating temperature is preferably at least 50°C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least 50°C and at most 100°C. Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may (Those listed in the section on formation accelerators are used)
can be mentioned. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt, and a complex-forming compound may be included in the solvent.

These solvents can be used in a method in which they are applied to a dye fixing element, a light-sensitive material, or both. The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating). As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A No. 61-147244 (2)
There is a method described on page 6). It is also possible to use the solvent by preliminarily incorporating it into the photosensitive material, the dye fixing element, or both, such as by encapsulating the solvent in microcapsules.

In order to promote dye transfer, a method may also be adopted in which a hydrophilic thermal solvent, which is solid at room temperature and dissolves at high temperature, is incorporated into the light-sensitive material or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing element.

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far-infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere. The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in JP-A-61-1.
The method described in No. 47244, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Utility Model No. 62-259
The apparatus described in No. 44 and the like is preferably used.

0099

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

Example 1 A photosensitive element having the structure shown in Table 1 was prepared and designated as photosensitive element 101. Next, a dye fixing material having the structure shown in Table 2-A was prepared and used as a dye fixing element (1). In addition, the dye fixing element ( 2) to (15) were created.

[0101]

[Table 1]

[0102]

[C36]

[0103]

[C37]

[0104]

[C38]

[0105]

[C39]

[0106]

[C40]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[C41]

[0113]

[C42]

[0114]

[C43]

[0115]

[C44]

The above photosensitive element and dye fixing material were processed using the image recording apparatus described in Japanese Patent Application No. 137104/1982. That is, an original image (a test chart recording wedges of yellow, magenta, cyan, and gray with continuously varying densities) is scanned and exposed through a slit, and the photosensitive element is placed in water kept at 40°C for about 50 minutes. After immersion for a second, the membrane was squeezed with a roller, and then immediately overlapped with the dye fixing material so that the membrane surface was in contact with the membrane surface, and heated for 25 seconds using a heat roller adjusted so that the temperature of the membrane surface that had absorbed water was 80°C. Next, when the photosensitive element and the dye-fixing element were peeled off, a clear color image corresponding to the original image was obtained on the dye-fixing material.

The amount of silver present in the Dmax portion of this image was measured using fluorescent X-rays. Furthermore, after desilvering using a bleach-fix solution used in conventional photographic processing, the minimum yellow density (Dmim) was measured. The measurement results are summarized in Table 3.

[0118]

[Table 7]

As can be seen from Table 3, the dye fixing materials using the compounds of the present invention had less silver stain than the comparative examples (1 to 3).

Furthermore, compound 55 of the present invention is added to the sixth layer of Table 1.
Photosensitive material 102 was prepared in the same manner as photosensitive element 101 except that -14 was added at 10 mg/m2. When this was used and treated in the same manner as in combination with dye fixing element (1),
The amount of silver present on the dye-fixing material was 4.6 mg/m2, which showed the same effect as the present invention, but the Dmin was high (0.243), which had a large effect on photographic properties. From the above, the effects of the present invention are clear.

[0121]

Effects of the Invention By using a dye fixing material containing the compound of the present invention, images free of silver stain can be obtained without increasing Dmin.

Claims (1)

[Claims] 1. An image forming method comprising diffusing and fixing a dye onto a support from a photosensitive element containing at least a photosensitive silver halide, a reducing agent and/or a reducing agent precursor, and a dye-providing compound. A dye-fixing element characterized in that the dye-fixing element contains an organic compound capable of forming a silver salt having a solubility product in water of pH 10 of 10-13 or less.