JPH0593994A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain the image forming method good in traveling performance and small in image forming trouble and capable of forming a positive color image especially high in image density and low in fog by overlaying a dye-fixing material on a photosensitive material in the presence of water and heating them in the image forming method. CONSTITUTION:The photosensitive material comprises on a support at least a photosensitive silver halide, a binder, an electron transferring agent, and a water-hardly-soluble basic metal compound, and the dye fixing material comprising on a support at least a binder, a mordant, a water-hardly-soluble basic metal metal compound, and a complex-forming compound containing an organic base and capable of forming a complex together with that metal compound in the presence of water is overlaid on that photosensitive material in the presence of water and heated to form an image by controlling the total amount of water contained in the photosensitive material and the dye fixing material to 8-18g/m<2> and imparting 30-65% of the total water into the photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method having a heating step, which has a good passage property in a processing apparatus, has few image failures, and is capable of obtaining a positive color image having high density and low fog. The present invention relates to an image forming method having a heating step that can be performed.

[0002]

2. Description of the Related Art Many methods have been proposed for forming a positive color image by heat development. Among them, U.S. Pat. Nos. 4,559,290 and 4,783 are proposed.
396, European Patent Publication 220,746, Public Technical Report 8
7-6199 (Vol. 12, No. 22), JP-A 64-134.
No. 56, ie, having on a support a photosensitive silver halide, an electron donor, a reducible dye-donating compound which is reduced by the electron donor to release a diffusible dye, and a binder. Heat development After heating the color light-sensitive material, it is heated to oxidize the electron donor according to the exposure amount of silver halide, and the electron donor left unoxidized reduces the reducible dye-donating compound and diffuses it. A promising method is to release a positive dye and transfer it to a dye fixing material having a mordant to form a positive color image.

In the patent specifications cited above, a light-sensitive material contains a basic metal compound which is poorly soluble in water, and a dye-fixing material uses a metal of the basic metal compound and water as a medium to form a complex-forming reaction. A compound that releases a base (hereinafter referred to as “complex forming compound”) is included, the photosensitive material is exposed to light, water is added, and then the dye-fixing material is superposed and heated to form an image. Aspects have been described.

In the heat-developable color light-sensitive material as described above, it is necessary to consume the electron donor by silver development in the exposed area as quickly as possible in order to suppress the stain of the color image. Therefore, a diffusible electron transfer agent is usually used in addition to the diffusion-resistant electron donor.

[0005]

The electron transfer agent as described above is preferably incorporated into the light-sensitive material in the form of fine particles in order to improve the raw storability of the electron transfer agent. Regarding the technology, JP-A-2-23014
As described in No. 3, when processing such a light-sensitive material, the distribution of water is biased toward the dye-fixing material side due to insufficient hardening of the dye-fixing material, etc. When the amount of water contained in the solution is reduced, there is a problem that the dissolution of the electron transfer agent is insufficient, the development is delayed, and the white background is deteriorated. On the contrary, when the distribution of water is biased to the side of the light-sensitive material and the amount of water contained in the dye-fixing material is substantially reduced, the complex-forming compound having an organic base is insufficiently dissolved, and However, there is a problem in that the image density is lowered due to the inefficient generation.

Furthermore, when the thickness of the support used for the photosensitive material is thin and the stiffness is weak, if the distribution of water deviates to the photosensitive material, the drying after peeling is insufficient and the curling becomes large, so that the processing apparatus There are problems such as extremely poor transportability in the interior and deterioration of the accumulation property of the waste photosensitive material. Furthermore, when water is deviated to either the light-sensitive material or the dye-fixing material, there is a problem that the adhesion is deteriorated and image unevenness occurs.

It is an object of the present invention to provide an image forming method capable of obtaining a positive color image having a high density and a low fog with few image defects.

[0008]

The above object of the present invention is achieved by an image forming method having the following configurations (1) and (2). (1) At least a photosensitive silver halide on a support,
A photosensitive material having a binder, an electron transfer agent, an electron donor, a reducible dye-donating compound that is reduced by the electron donor to release a diffusible dye, and a basic metal compound that is poorly soluble in water, and a support In the presence of water, at least a binder, a mordant, and a dye-fixing material having a complex-forming compound having an organic base, which can form a complex with a water-insoluble basic metal compound and water as a medium, are formed on the body in the presence of water. In an image forming method including a heating step of superposing and heating, the total amount of water contained in the light-sensitive material and the dye fixing material at the time of superposing and heating is 8 g / m ² to 18 g / m ² , and 3
An image forming method including a heating step, characterized in that 0% or more and 65% or less is contained in a light-sensitive material. (2) The total thickness of the support used for the photosensitive material is 150 μm.
An image forming method including the heating step described in the above (1), which is as follows.

The present invention will be described in detail below. The photosensitive material and dye fixing material used in the image forming method of the present invention are
Both contain a hydrophilic binder and are hardened with a hardener.

In the image forming method of the present invention, the total amount of water contained in the light-sensitive material and the dye-fixing material at the time of superposition heating is adjusted to 8 to 18 g / m ² , and the amount of water is 30.
It is important to adjust the content of the light-sensitive material to be contained in an amount of up to 65%. For example, as a means for adjusting the contact time between the light-sensitive material and water for imparting water to the light-sensitive material and the temperature thereof, The coating amounts of the hydrophilic binder (eg gelatin) and the hardener used for the light-sensitive material, the coating amount of the hardener used for the dye fixing material, and the balance between them are important. Particularly, the coating amount of the hydrophilic binder or the hardener is important. That, is preferably in the range of coating amount of from 1 to 20 g / m ² of hydrophilic binder used in the photosensitive material (such as gelatin), more preferably in the range yet 1.5~10g / m ^2, in particular 2~7g The optimum range is / m ² . Further, the coating amount of the hydrophilic binder (eg gelatin) used for the dye fixing material is not particularly limited, but 1
The range of 10 to 10 g / m ² is desirable. Further, the coating amount of the hardener varies depending on the kind of the hardener used and the kind of the binder.
The range of mg / m ² is preferable, and particularly 10 to 1
A range of 50 mg / m ² is preferred. The coating amount of hardener used in the dye-fixing material is preferably in the range of 80~900mg / m ^2, in particular in the range of 100 to 600 mg / m ² is preferred. As a balance of these, for example,
The hardening degree of the light-sensitive material layer and the dye-fixing material layer is mentioned, and this hardening degree is determined by the amount of the hardening agent with respect to the amount of the hydrophilic binder coated. In this preferable range, in the light-sensitive material, the total amount of the hardener is 3 mg to 50 mg, and more preferably 7 mg to 20 mg per 1 g of the hydrophilic binder.
In the dye-fixing material, the total amount of the hardener is 10 mg to 800 mg per 1 g of the hydrophilic binder.
More preferably, it is in the range of 70 mg to 500 mg. The amount of the hardener added per 1 g of the hydrophilic binder of the light-sensitive material and the dye-fixing material may be 1.5 to 8 times the value of the dye-fixing material as compared with the value of the light-sensitive material. The range is more preferably 2 to 5 times.

As an example of the hydrophilic binder used in the light-sensitive material and the dye-fixing material, there is disclosed in JP-A-62-25315.
Examples thereof include those described in No. 9, pages (26) to (28). Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Further, superabsorbent polymers described in JP-A-62-245260, that is, -COOM or-
A homopolymer of a vinyl monomer having SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more.

As a hardener used in the constituent layers of the light-sensitive material and the dye-fixing material, US Pat. No. 4,678,739, No. 4
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners (exemplified compounds as shown in Chemical formula 1), vinyl sulfone type hardeners (N, N '). -Ethylene-bis (vinylsulfonylacetamide) ethane etc.), N-methylol type hardeners (dimethylol urea etc.), or polymer hardeners (compounds described in JP-A-62-234157). Be done.

[0013]

[Chemical 1]

The light-sensitive material used in the image forming method of the present invention is basically a photosensitive silver halide, a binder, an electron transfer agent, an electron donor and a diffusible material which is reduced by the electron donor on a support. It has a reducible dye-donating compound that releases a dye, and may further contain an organometallic salt oxidizing agent and the like, if necessary. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a dye-providing dye compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. Although the electron transfer agent is incorporated in the photothermographic material, it may be used in combination with a method of supplying it from the outside, for example, by a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having light sensitivity in different spectral regions is used. .. For example, there are combinations of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photothermographic material comprises a protective layer, an undercoat layer,
Various auxiliary layers such as an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

The silver halide usable 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 either 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 a light fogging. Further, it may 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, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or any other shape. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods, selenium sensitizing methods and the like can be used alone or in combination for emulsions for conventional type light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-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.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and 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. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) Sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

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, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate;
The acetylene silver described in 1-24944 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957 and the like can be used.

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 which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, and U.S. Pat. No. 4,483,914, columns 30 to 31.
Column, No. 4,330,617, No. 4,590,152
Nos. (17) to (1) of JP-A-60-140335.
8), pages 57-40245, 56-138736.
No. 59-178458, No. 59-53831,
59-182449, 59-182450, 60-119555, 60-128436 to 60-128439, 60-198540,
No. 60-181742, No. 61-259253, No. 62-244044, No. 62-131253 to No. 62-131256, European Patent No. 220,746.
There are reducing agents and reducing agent precursors described on pages 78 to 96 of A2. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent is optionally added 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 above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has a mobility higher 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 that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinones, Examples thereof include sulfonamide phenols, sulfonamide naphthols, and the compounds described as electron donors in JP-A No. 53-110827. In the present invention, the amount of the reducing agent added is 0.00 per mol of silver.
It is 1 to 20 mol, particularly preferably 0.01 to 10 mol.

Examples of the dye-donating compound which can be used in the present invention include compounds having a function of releasing or diffusing a diffusible dye imagewise. 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 linking group, and Z represents an image latent image. Inversely corresponding to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) _n -Z, or releasing Dye, and released Dye and (Dye-Y) represents a group having a property of causing a difference in diffusibility from _n- Z, and n is 1
Or, it represents 2 and when n is 2, two Dye-Ys may be the same or different. Specific examples of the dye-donating compound represented by the general formula [LI] include US Pat.
59,290, European Patent 220,746A2, US Pat. No. 4,783,396, Open Technical Report 87-619.
As described in 9, etc., a non-diffusible compound that reacts with the reducing agent remaining without being oxidized by development to release a diffusible dye can be used.

As an example thereof, US Pat. No. 4,139,
389, 4,139,379, JP-A-59-18.
Compounds that release diffusible dyes by nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107.
JP-A-59-101649 and 61-88257.
, RD24025 (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, US Pat. No. 4,343,
893, 4,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, electron acceptors described in US Pat. No. 4,450,223, etc. Nitro compounds, which later release diffusible dyes,
Examples thereof include compounds described in US Pat. No. 4,609,610 which release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, No. 63-201654 and the like, compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-161342, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,783,3.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64), (70), compounds (11) to (23) described in Public Technical Report 87-6199, and the like.

Hydrophobic additives such as dye donating compounds and diffusion resistant reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453 and 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g, per 1 g of the dye-donor compound used.
It is below. Further, 1 cc or less, further 0.5 cc or less, and particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid as the binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

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

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be applied separately on a support different from the photosensitive element or may be applied on the same support as the photosensitive element. Regarding the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. In order to include such a form in which the light-sensitive element and the dye-fixing element are coated on the same support, the light-sensitive material used in the present invention will be described below mainly for the sake of convenience, using the terms of the light-sensitive element. .. The dye fixing element is also called a dye fixing material.

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 US Pat. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (3)
2) to (41), the mordants described in JP-A-62-244.
No. 043, No. 62-244036, etc. can be mentioned. Also, U.S. Pat. No. 4,463,07
A dye-accepting polymer compound as described in No. 9 may be used. The dye fixing element may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of promoting the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, it is a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver. Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned promoting effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Base precursors that can be used in the present invention include European Patent Publication No. 210,660, US Pat.
A combination of a sparingly soluble metal compound described in No. 740,445 and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound) can be used. The sparingly soluble metal compound and the complex-forming compound are
It is advantageous to add them separately to the light-sensitive element and the dye-fixing element.

In the present invention, various development terminators can be used in the light-sensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base after proper development to lower the concentration of the base in the film to stop the development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof 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. More specifically, JP-A-62-25
No. 3159, pages (31) to (32).

The constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element are for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. ..

In the constituent layers of the light-sensitive element and the dye-fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" Technical Material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) and the like are effective. In addition, JP-A-62
The silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. As the antioxidant, for example, chroman compounds, coumarans compounds,
Phenolic compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds are available. In addition, JP-A-61
The compounds described in No. 159644 are also effective. Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681), benzophenone compounds (JP-A-46- 2784) and others, JP-A-54-48535 and JP-A-62-136641.
No. 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,245,018, Nos. 3 to 4.
36 column, 4,254,195, columns 3-8, JP-A-6
No. 2-174741, No. 61-88256 (27)-
(29), 63-199248, JP-A-1-75.
There are compounds described in Nos. 568 and 1-74272. Examples of useful anti-fading agents are disclosed in JP-A-62-215.
272 (125)-(137).

The anti-fading agent for preventing the 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 the outside such as a light-sensitive element. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the light-sensitive element and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light sensitive element. As an example, K. Veenkataraman
Edited by "The Chemistry of Synthes"
tic Dyes "Vol. V, Chapter 8, JP-A-61-143
Examples thereof include compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of static charge, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, etc., or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil, or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Is mentioned.

A matting agent can be used in the light-sensitive element and the dye-fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, a support that can withstand the processing temperature is used as the support for the light-sensitive element and the dye-fixing element. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate (PET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and polypropylene. Film method synthetic paper made from
Mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene.
In addition to this, JP-A-62-253159 (29) to (3)
The support described on page 1) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

Examples of the method for exposing and recording an image on a light-sensitive element include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or an 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 through an electric signal, a CRT, a liquid crystal display, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on the photosensitive element,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also 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 nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and compounds described in JP-A Nos. 61-53462 and 62-210432 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. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. Signals, image signals created by using a computer represented by CG, CAD can be used.

The heating temperature in the heat development step is preferably about 50 ° C. or more and 100 ° C. or less, more preferably 60 ° C. or more 9
It is in the range of 0 ° C or lower.

The water used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer contains a surfactant,
An antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained.

A method for applying water to the photosensitive layer or the dye fixing layer is described in, for example, JP-A-61-147244 (2).
6) There is a method described on page. Further, it can be used by preliminarily incorporating it in a light-sensitive element or a dye-fixing element or both in the form of confining water in microcapsules.

Further, in order to accelerate the dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive element or the dye-fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. 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 its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to accelerate dye transfer, a high boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. Or passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and electricity may be applied to the resistance heating element layer to heat it. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye fixing element,
For the pressure condition and the method of applying the pressure for the close contact, see Japanese Patent Laid-Open No.
The method described on page 27 of 1-147244 can be applied.

Any of a variety of heat developing apparatus can be used in processing 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, No. 62-259
The device described in No. 44 etc. is preferably used.

[0050]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 A method for preparing a zinc hydroxide dispersion will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of 4% gelatin aqueous solution.
In addition, the mixture was pulverized with a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. Chemical formula 2 electron transfer agent 10g, polyethylene glycol nonyl phenyl ether 0.5g as a dispersant,
And 0.5 g of the anionic surfactant of Chemical formula 3 were added to 100 ml of 5% gelatin aqueous solution, and the average particle size was 0.75 with a mill.
Milled for 60 minutes using mm glass beads. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.4 μm.

[0053]

[Chemical 2]

[0054]

[Chemical 3]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. According to the formulation of Table A below, the dye-providing compounds of yellow, magenta, and cyan were respectively added.
It was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 m of water
l after stirring and mixing, 10 minutes with a homogenizer, 10
Dispersed at 000 rpm. This dispersion is called a gelatin dispersion of a dye-donor compound.

[0056]

[Table 1]

The dye-donating compounds (1), (2), (3) and (4) in Table A are shown in Chemical formula 4, Chemical formula 5, Chemical formula 6 and Chemical formula 7, respectively, and electron donors ( 1) is shown in Chemical formula 8, high-boiling point solvent (2) is shown in Chemical formula 9, and electron transfer agent precursor (3) is shown in Chemical formula 10.

[0058]

[Chemical 4]

[0059]

[Chemical 5]

[0060]

[Chemical 6]

[0061]

[Chemical 7]

[0062]

[Chemical 8]

[0063]

[Chemical 9]

[0064]

[Chemical 10]

Next, a method for preparing a gelatin dispersion of the electron donor (4) for the intermediate layer will be described. 20.0 g of the electron donor (4) of Chemical formula 11, 5.9 g of the compound (5) of Chemical formula 12, 1.8 g of the compound (6) of Chemical formula 13, and further 8.5 g of the high-boiling solvent (2) of Chemical formula 9, Cyclohexanone (13 ml) and ethyl acetate (30 ml) were added, and the mixture was heated and dissolved at 60 ° C to obtain a uniform solution. 10% aqueous solution of this solution and lime-processed gelatin 1
00g, sodium dodecylbenzenesulfonate 0.8g,
After stirring and mixing 0.3 g of sodium hydrogen sulfite and 30 ml of water, a homogenizer was used for 10 minutes for 10,000.
Dispersed at rpm. This dispersion is called a gelatin dispersion of the electron donor (4).

[0066]

[Chemical 11]

[0067]

[Chemical formula 12]

[0068]

[Chemical 13]

Next, a method for preparing a photosensitive silver halide emulsion will be described. Light-sensitive silver halide emulsion (I) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride, and chemical agent (A) of chemical formula 14 in 480 ml of water. Add 30 mg and 45
The solution (I) and the solution (II) of Table B were simultaneously added at a constant flow rate over 20 minutes. Thereafter, the solutions (III) and (IV) in Table C were simultaneously added over 25 minutes. Further, 10 minutes after the addition of the solutions (III) and (IV) in Table C was started, the following dye solution was added over 20 minutes. Washing with water,
After desalting, add 22 g of lime-treated ossein gelatin and add pH
Was adjusted to 6.2 and pAg was adjusted to 7.7, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C. Thus the average particle size of 0.3
A 0 μm monodisperse cubic silver chlorobromide emulsion was obtained. Yield 635
It was g.

[0070]

[Chemical 14]

[0071]

[Table 2]

[0072]

[Table 3]

Dye solution 67 mg of the dye (a) of the chemical formula 15 and 13 of the dye (b) of the chemical formula 16
3 mg and 4.4 mg of the dye (c) of Chemical formula 17 dissolved in 100 ml of fluorinated alcohol.

[0074]

[Chemical 15]

[0075]

[Chemical 16]

[0076]

[Chemical 17]

Photosensitive Silver Halide Emulsion (II) [For Green Sensitive Emulsion Layer] Well stirred aqueous solution (20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride in 730 ml of water).
And 0.015 g of the chemical (A) of Chemical formula 14 was added to 60.
6) of solution I and solution II in Table D at the same time.
Add at equal flow rate over 0 minutes. After the addition of solution I,
In a methanol solution of the sensitizing dye (d) of Formula 18 and III in Table D
The liquid was added. Thus the average particle size 0.45
A monodisperse cubic silver chlorobromide emulsion adsorbing a μm dye was prepared. After washing with water and desalting, 20 g of gelatin was added to adjust pH to 6.4 and pAg to 7.8, and then chemical sensitization was performed at 60.0 ° C. The chemicals used at this time were 1.6 mg of triethylthiourea and 4-hydroxy-6-methyl-1,
The aging time was 55 minutes with 100 mg of 3,3a, 7-tetrazaindene. The yield of this emulsion is 635g.
Met.

[0078]

[Table 4]

[0079]

[Chemical 18]

Photosensitive silver halide emulsion (III) [for blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 3 g of potassium bromide, and HO (CH ₂ ) in 800 ml of water)
The ₂ S (CH _{2) 2} S (CH _{2) 2} OH and those kept by adding 0.3g to 55 ° C.), was added over Table E of (1) solution and (2) fluid simultaneously for 30 minutes. Thereafter, the solutions (3) and (4) in Table E were simultaneously added over 20 minutes.
Further, the dye solution described below was added in 18 minutes from 5 minutes after the addition of the solutions (3) and (4) in Table E was started. After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2,
The pAg was adjusted to 8.5 and then adjusted to 4 with sodium thiosulfate.
Optimum chemical sensitization was performed by adding -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and chloroauric acid. In this way, monodisperse particles having an average particle size of 0.40 μm
600 g of a surfaced silver iodobromide emulsion was obtained.

[0081]

[Table 5]

Dye solution 0.12 g of the dye (e) of the chemical formula 19 and the dye (f) of the chemical formula 20
0.12 g dissolved in 160 ml of methanol.

[0083]

[Chemical 19]

[0084]

[Chemical 20]

Photosensitive material 1 shown in Table F using the above
I made 01.

[0086]

[Table 6]

[0087]

[Table 7]

In Table F, the support (1) had only the constitution as shown in Table G, and the compounds (7), (12)
Is represented by Chemical formula 21, antifoggant (8), (1
1) is represented by Chemical formula 22, hardeners (9), (10)
Is represented by Chemical formula 23, and the compound (13) is represented by Chemical formula 24.

[0089]

[Table 8]

[0090]

[Chemical 21]

[0091]

[Chemical formula 22]

[0092]

[Chemical formula 23]

[0093]

[Chemical formula 24]

Next, the amounts of the hardeners (9) and (10) added to the fourth layer of the photosensitive material 101, the second layer and the fourth layer
The light-sensitive material 101 was prepared in the same manner as in the light-sensitive material 101 except that the amount of lime-processed gelatin added to each of the layers and the sixth layer was as shown in Table H.
Photosensitive materials 102-105 were made.

[0095]

[Table 9]

Further, in the same manner as the photosensitive materials 101 to 105, except that the support (2) shown in Table I is used instead of the support (1) of the photosensitive materials 101 to 105,
Photosensitive materials 201 to 205 were prepared.

[0097]

[Table 10]

Next, how to make the image receiving material will be described. An image receiving material 301 having a constitution as shown in Table J was prepared.

[0099]

[Table 11]

In Table J, the support (3) has the constitution as shown in Table K, and the compound is as shown in Chemical formula 25 as silicone oil and as the surfactant.
Those shown in Chemical formula 27 as mordants,
The high boiling point solvent is shown in Chemical formula 28, and the hardener is shown in Chemical formula 29.

[0101]

[Table 12]

[0102]

[Chemical 25]

[0103]

[Chemical formula 26]

[0104]

[Chemical 27]

[0105]

[Chemical 28]

[0106]

[Chemical 29]

The matting agent, water-soluble polymer and optical brightening agent in Table J are shown below. Matting agent (1); silica Matting agent (2); Benzoguanamine resin (average particle size 15
μm) Water-soluble polymer (1); Sumikagel L5-H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2); Dextran (molecular weight 70,000) Optical brightener (1); 2,5-bis (5-) Tertiary butyl benzoxazolyl (2)) thiophene

Next, the image receiving material 302 was prepared in the same manner as the image receiving material 301 except that the coating amount of the hardener (1) added to the first layer of the image receiving material 301 was changed to the amount shown in Table L.
I made ~ 304.

[0109]

[Table 13]

The above light-sensitive materials 101 to 105, 201 to
205 and the image receiving materials 301 to 304 are disclosed in JP-A-2-
Processing was performed using the image recording device described in No. 84634.
That is, the original image [Y, M, whose density is continuously changing,
The test chart on which Cy and gray wedges are recorded] is scanned and exposed through a slit, and the exposed light-sensitive material is dipped in water kept at 40 ° C. for 3 seconds, squeezed with a roller, and immediately thereafter as an image receiving material. The layers were superposed so that the film surfaces were in contact with each other. The temperature of the film surface that absorbed water is 78 ℃
By heating for 15 seconds using a heat drum whose temperature was adjusted so that it was peeled off from the light-sensitive material, a clear color image corresponding to the original image was obtained on the image-receiving material. With respect to these color images, the density of the gray wedge portion was measured.

Next, using the above-described processing apparatus, the light-sensitive material was immersed in water kept at 40 ° C. for 3 seconds, squeezed with a roller, and immediately thereafter, the image-receiving material and the film surface were superposed so that they were in contact with each other. After heating for 15 seconds using a heat drum whose temperature was adjusted so that the water-absorbed film surface became 78 ° C., the light-sensitive material and the image-receiving material were peeled off, and the amount of water contained in the light-sensitive material and the image-receiving material was measured.

Furthermore, the above processing apparatus was brought into an environmental test room, and a pass test was conducted on 500 sheets of each under the environment of 30 ° C. 80% RH and 10 ° C. 20% RH. The results are shown in Table M.

[0113]

[Table 14]

[0114]

[Table 15]

As is clear from the results shown in Table M, in Experiment No. 1 in which the amount of water contained in the light-sensitive material during the developing process was too small.
In Experiment Nos. 2, 7, and 11, Dmin was high, and Experiment No. 1 in which the amount of water was too large. In Nos. 3 and 8, Dmax is low. In addition, in Experiment No. 1 in which the water amounts of the light-sensitive material and the image-receiving material were poorly balanced.
In Nos. 3, 7, 8, 11, and 12, image unevenness occurs. Further, when the support has a thickness of 150 μm or less, the test No.
It can be seen that defective passage occurs like 7, 8, 11, and 12. Thus the cure of the present invention is clear.

[0116]

According to the present invention, the total amount of water contained in the light-sensitive material and the dye-fixing material at the time of stacking and heating is 8 to 18 g.
/ M ² and by adjusting so that 30 to 65% thereof is contained in the light-sensitive material, a color image with high image density and low fog can be obtained without image unevenness and failure during image processing. It was obtained stably.

Claims (2)

[Claims] 1. A photosensitive silver halide, a binder, an electron transfer agent, an electron donor, a reducible dye-donating compound which is reduced by the electron donor to release a diffusible dye, on a support. And a light-sensitive material having a water-insoluble basic metal compound, at least a binder on a support, a mordant, and a complex formation of the water-insoluble basic metal compound with water as an organic base. In the image forming method including a heating step of heating the dye-fixing material having the complex-forming compound having the above in the presence of water, the total amount of water contained in the photosensitive material and the dye-fixing material at the time of overlay heating is 8 g / An image forming method including a heating step, characterized in that the light-sensitive material contains m ² to 18 g / m ² and 30% or more and 65% or less thereof. 2. The total thickness of the support used for the light-sensitive material is 15
The image forming method including the heating step according to claim 1, wherein the image forming method is 0 μm or less.