JPH0876332A - Heat treatment of heat developable photographic element - Google Patents

Abstract

PURPOSE: To uniformly heat a heat developable photographic element swollen with water or a processing liquid and to obtain a uniform image high in density by heat-treating the photographic element swollen with water or a processing liquid while bringing the element into contact with a heated inert liquid. CONSTITUTION: A photographic element swollen with water or a processing liquid is heat-treated by bringing it into contact with a heated inert liquid. In this case, just after exposure or after heat treatment of the photographic element, water or a water-soluble processing liquid containing a photographic effective material is imparted to the photographic element. For example, in order to accelerate development and/or to move a diffusive dyestuff to a dyestuff fixing layer, water or a basic soln. containing alkali metal salt or org. base is imparted to the element. Or, a mixture of a solvent having low boiling point and water or a basic soln. can be used. Moreover, a surfactant, fog preventing agent, compd. which forms a complex with hardly-soluble metal salt, reducing agent, fixing agent, bleach fixing agent or the like may be added to the solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a method of heat treating a photographic element which has been swollen with water or a processing liquid, and in particular in the presence of a small amount of water, imagewise from a photosensitive element containing a photosensitive silver halide. The present invention relates to a heat development processing method for a photographic element for black and white or color image formation in which a diffusible dye formed is diffused and fixed on a dye fixing element.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photographic method in photographic characteristics such as sensitivity and gradation control. Came. In recent years, it has become possible to easily and quickly obtain an image by changing the image forming method of the photosensitive element using silver halide from the conventional wet processing using a developing solution or the like to dry processing such as heat processing or pod expansion processing. Techniques have been developed that can.

In such an image forming method by rapid processing, desilvering processing is difficult, so that a diffusion transfer method which does not require this desilvering processing step is often used. As a color photosensitive element using this method, a typical example is an instant color photograph which is currently commercialized,
For more information on this technique, see Angero. Chem.
Int. Ed. Engl., 22 , 1983, 191-
209; Imag. Tech., 15, 3, Jun
e, 1989 etc. Further, in many of the heat-developable color photosensitive elements that have been developed in recent years, the diffusion transfer method is often used.

Photothermographic elements are well known in the art, and the photothermographic element and its process are described, for example, in "Basics of Photographic Engineering", Non-silver Salt Photographs, 1982, pages 242 to 255. It is described in. U.S. Pat. Nos. 4,500,626 and 4,483,914 are used for a heat-developable color photosensitive element using a diffusion transfer method.
No. 4,503,137, 4,559,920
And JP-A-59-165054, there is a description of a negative type system. In the above method, the developing temperature is high, and the temporal stability of the photosensitive element cannot be said to be sufficient. Therefore, heat development is performed in the presence of a base or a base precursor and a small amount of water to accelerate the development by transferring the dye.
A method for reducing the developing temperature and simplifying the processing is disclosed in Japanese Patent Laid-Open No. 59-59
-218443, 61-238056, and European Patent 210,660A2.

Many methods have been proposed for obtaining a positive color image by heat development. For example, U.S. Pat. No. 4,559,290 proposes a method of using a so-called DRR compound in an oxidized form having no dye releasing ability. That is, in the presence of a reducing agent or its precursor, the reducing agent is oxidized by thermal development according to the exposure amount of silver halide, and the oxidized DRR compound is reduced by the reducing agent remaining without being oxidized. This is a method of releasing a diffusible dye. US Pat. No. 4,783,396
No., European Patent Publication No. 220,746, Technical Report 87-6
In 199 (Vol. 12, No. 22), a compound that releases a diffusible dye by a similar mechanism is diffusible by reductive cleavage of an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom). Photothermographic color light-sensitive elements using dye-releasing compounds are described.

Further, in order to carry out a simple and quick process at a lower cost, a monosheet type image forming photographic element having a light-sensitive element and a dye fixing element on the same support has been proposed. For example, in JP-A-61-93451, (1) transparent or opaque support / photosensitive layer / white reflective layer / dye fixing layer, or (2) transparent support / dye fixing layer / white reflecting layer / photosensitive Layers and the like are described.

[0007]

However, the following problems exist when the above-mentioned photographic element is subjected to the heat development treatment after supplying a small amount of water. (1) When the coated film surface is heated in an open state (for example, high frequency heating), water is evaporated during heating, a sufficient heat development reaction does not occur, and partial evaporation causes unevenness at low concentration. An image is formed. (2) In the method in which the coated film surface is superposed on the surface of a hot plate or the like and heated, the photographic element adheres to the heating means, and the conveyance is apt to occur. Further, when the heat development process is repeated, the heat plate becomes dirty, resulting in uneven heat development, which leads to image unevenness. Furthermore, it is not preferable in terms of maintenance. (3) In order to prevent evaporation of water, there is a method in which a film or the like is superposed on the surface of the coating film and subjected to heat development treatment, but this method is not preferable in terms of environmental protection and cost because the film is discharged as waste. (4) When the light-sensitive element and the dye-fixing element are coated on separate supports, after water is applied to one or both of them, they are superposed and passed through a heat roller or pressed against a hot plate to heat. When development transfer is carried out, water oozes out from the edge of the photographic element to which water is applied, and the heat roller or hot plate is soiled, causing image unevenness and the like. (5) Heating with a hot plate or a heat roller tends to cause image unevenness due to uneven temperature distribution.

[0008]

OBJECTS OF THE INVENTION Accordingly, it is an object of the present invention to provide a method of heat treating a photothermographic element swollen with water or a processing solution. Another object of the present invention is to provide a heat treatment method capable of uniformly heating a mono-sheet type or two-sheet type photothermographic image forming photographic element swollen with water or a treatment liquid to obtain a uniform and high density image. It is in. A further object of the present invention is to provide a method for heat-treating a mono-sheet type or two-sheet type heat-developable image forming photographic element swollen with water or a processing solution in a waste-free and easy-maintenance method. is there.

[0009]

SUMMARY OF THE INVENTION The above-mentioned object is to provide a heat-developable photographic element characterized by subjecting a photographic element swollen with water or a processing solution to heat treatment by bringing it into contact with a heated inert liquid. This is achieved by a heat treatment method.

The photographic elements used in this invention are provided with a water-soluble processing solution containing water or a photographically useful substance immediately after exposure or after heat treatment. For example, in order to accelerate development and / or transfer the diffusible dye to the dye fixing layer, water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image formation accelerator The one described in the section is used) is added. Alternatively, a mixed solution of a low boiling point solvent and water or a basic water-soluble solvent can be used. Further, a surfactant, an antifoggant, a compound which forms a complex with a poorly soluble metal salt, a reducing agent, a fixing agent, a bleach-fixing agent and the like may be contained in the solvent. The amount of these water or aqueous solution applied is not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film of the photographic element (particularly the weight of the entire coating film is subtracted from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film). Less than amount)
Good. As a method of applying water or an aqueous solution to a photographic element, for example, JP-A-61-147244, (2)
6) There is a method described on page.

The inventor of the present invention disclosed a method of using an inert liquid as a heating method for a completely dry type photothermographic material in Japanese Patent Application Laid-Open No. 61-9649. After that, a small amount of water was applied to the photographic element, and various methods of uniformly heating the sufficiently swollen monosheet type or two-sheet type photographic element were examined. In the present photographic element as well, it was found that by contacting with the heated inert liquid, the previously applied water is uniformly heated without being lost due to evaporation etc., and as a result, a uniform image can be formed. I arrived.

The inert liquid used in the present invention is such that it normally allows a liquid such as water to pass through it and allows it to pass through a swollen photographic element, so that it does not damage the photographic element at all. It is necessary that the liquid has a large thermal conductivity and is suitable for thermal development. It must be a liquid that does not get wet (compatible) at all when it comes into contact with photographic elements that contain oil and water-soluble substances as well as water and water-soluble substances and that only transfers heat. Such liquids include hydrocarbon fluorides and developing temperatures of mercury, gallium, etc. (5
Examples thereof include liquid metals (including alloys) at 0 to 100 ° C., among which fluorocarbons having a high fluorination rate are preferable, and perfluorocarbons are particularly preferable. Further, a fluorocarbon having a boiling point of 100 ° C. or higher, further 120 ° C. or higher, and particularly 140 ° C. or higher is preferable.

Specific examples of the inert liquid which can be used in the present invention include Fluorinert (registered trademark of US 3M Company) manufactured by US 3M Company. For example, FC40 (boiling point 155 ° C), FC43 (boiling point 174)
℃), FC70 (boiling point 215 ℃), FC71 (boiling point 25
3 ° C). Since this substance has a completely fluorinated structure, it is almost insoluble in water and oil.
Its thermal conductivity is large, and is twice as high as that of silicone oil during heat transfer by natural convection, and 5 times as high as that of forced air. Therefore, even when the photographic element is passed through the photographic element, the photographic element and the Fluorinert repel each other, and the photographic element is efficiently heated and transferred without any damage.

Higher heating temperatures of the inert liquid can reduce the contact time between the photographic element and the inert liquid, thus reducing the size of the inert liquid bath.
Above 0 ° C, water is boiled and lost, which is not preferable and may cause decomposition of the inert liquid.
Therefore, the inert liquid used in the present invention is 50 ° C to 100 ° C.
C., preferably in the temperature range of 70 to 98.degree.

The photographic elements used in the present invention include all that need to be provided with water or an aqueous solution containing a photographically useful substance and to be heated. Specific examples include photographic elements having the following configurations, but the present invention is not limited to these. (1) A dye fixing element for fixing a diffusible dye released or formed by heat development in a light-sensitive element on a transparent support, a white reflective layer, at least silver halide, a colorless dye for forming or releasing a diffusible dye. A photographic element in which light-sensitive elements containing a dye-providing substance and a hydrophilic binder are sequentially laminated. (2) On a transparent support or a white support for a reflective material, a dye fixing element for fixing a diffusible dye released or formed by heat development in a photosensitive element, a peeling layer, at least silver halide, and a diffusible dye are formed. A photographic element in which light-sensitive elements containing a dye-providing substance and a hydrophilic binder are sequentially laminated. After thermal development, the photosensitive element is peeled off.

(3) A photosensitive element containing, on a support, at least a silver halide, a dye-providing substance capable of forming or releasing a diffusible dye by heat development and a hydrophilic binder.
A photographic element in which a layer which becomes transparent at the time of exposure, becomes opaque by a heat treatment after exposure or after heat development and becomes a white reflective layer, and a dye fixing element for fixing a dye diffused from a photosensitive element are sequentially laminated. (4) On a transparent support, at least silver halide, a light-sensitive element containing a dye-donor substance capable of forming or releasing a diffusible dye by heat development and a hydrophilic binder, a white reflective layer, and a light-sensitive element diffused from the light-sensitive element. A photographic element in which dye-fixing elements for fixing dyes are sequentially laminated. (5) A light-sensitive element containing at least a silver halide, a dye-donating substance capable of forming or releasing a diffusible dye by heat development, and a hydrophilic binder on a support, and a light-sensitive element diffused on another support from the light-sensitive element. It consists of two elements, a dye fixing element containing a dye fixing agent that fixes the incoming dye. After exposure,
Water is applied to one or both of them, and both are overlapped and heated to perform a heat development transfer process.

Next, the photosensitive element, dye fixing element, white reflecting layer and peeling layer used in the above (1) to (5) will be described.

The light-sensitive element of the present invention basically has a light-sensitive silver halide, a dye-donor compound (which may also serve as a reducing agent as described later), and a binder, and further, if necessary. An organic metal salt oxidizing agent and the like can be included. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the light-sensitive element, but may be supplied from the outside by, for example, a method of diffusing from a dye-fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram 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 a combination of three layers of 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 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 photosensitive element can be provided with various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer.

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 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 an optical 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 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of silver halide grains is cubic, octahedral, 14
It may be a face piece, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19)
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 in an unripened state, but is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). 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 especially for the purpose of supersensitization. A dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light, together with a sensitizing dye,
A compound exhibiting supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641 and JP-A-63-231).
No. 45 etc.).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or in accordance with US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after formation. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the light-sensitive element of the present invention, an organic metal salt may be used as an oxidizing agent together with the light-sensitive 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 phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 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 in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

As the reducing agent used in the present invention, those known in the field of photosensitive materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits 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 49-50, 4,483,914, columns 30-31, 4,3.
No. 30,617, No. 4,590,152, and Japanese Patent Laid-Open No. Sho 6
0-140335, pages (17) to (18), ibid. 57.
-40245, 56-138736, 59-1
78458, 59-53831, 59-182.
No. 449, No. 59-182450, No. 60-1195.
55, 60-128436 to 60-1284
39, 60-198540, 60-181
No. 742, No. 61-259253, No. 64-2440.
No. 44, No. 62-131253 to No. 62-1312
Up to 56, 78 of EP 220,746A2
No. 96 and the like are reducing agents and reducing agent precursors. 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 may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols. The electron transfer agent is a compound that easily diffuses and moves. Therefore, the present invention exerts a great effect particularly in preventing coloring due to the transfer of the electron transfer agent to the dye fixing element.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the photosensitive element.
Preferred are hydroquinones, sulfonamide phenols, sulfonamide phenols, JP-A-53-11.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below. In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.01 to 10 mol, based on 1 mol of silver.

In the present invention, a compound that produces or releases a movable dye in response to the exposure amount or inversely corresponding thereto, that is, a dye-donating compound is used. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers are described in "The Theory of the Photographic Process", 4th edition by James (T.
H. James "The Theory of Photo"
graphical Process ") 291-334
Pages, and pages 354 to 361, JP-A-58-12353.
No. 3, No. 58-149046, No. 58-149047.
No. 59-111148 and 59-124399.
No. 59-174835, 59-231539.
No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2.
No. 3474, No. 60-66249 and the like.

As another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [L1]. (Dye-Y) _n -Z [L1] [Dye represents a dye group, generally a shortened dye group or dye precursor group, Y represents a simple bond or a linking group, and Z represents an image latent image. The compound represented by (Dye-Y) _n -Z is made to have a difference in diffusivity corresponding to or opposite to the photosensitive silver salt having an image, or Dye is released, and the released Dye and (Dye -Y) _n- Z represents a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. May be. ]

Specific examples of the dye donating compound represented by the general formula [L1] include the following compounds (1) to (3). In addition, the following items (1) to (5) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and is the diffusible dye image (positive dye image) corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764, 3,362,819, and 3,597,200,
A dye developing agent described in U.S. Pat. No. 3,544,545, U.S. Pat. No. 3,482,972 and the like, in which a halodroquinone-based developer and a dye component are linked. This dye developing agent is diffusible under an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. . Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479 and isoxazolones described in US Pat. No. 4,199,354. Examples of the compound include a compound that releases a diffusible dye by an intramolecular rewinding reaction of the ring.

US Pat. No. 4,559,290, European Patent 220,746A2, Open Technical Report 87-619
As described in 9 and the like, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. For example, US Pat. No. 4,
139,389, 4,139,379, JP-A-59-185333, JP-A-57-84453, etc., and a diffusible dye is obtained by a nucleophilic substitution reaction in the molecule after reduction. Releasing Compound, US Pat. No. 4,23
2,107, JP-A-59-101649, 61-
88257, RD24025 (1984) and the like, compounds that release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent 3,008,5
88A, JP-A-56-142530, U.S. Pat. Nos. 4,343,893, 4,619,884, etc., and the single bond is cleaved to release a diffusible dye after reduction. Compounds, nitro compounds described in US Pat. No. 4,450,223, which release diffusible dyes after electron acceptance, US Pat. No. 4,609,610, etc., diffusible dyes after electron acceptance And compounds that release

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199,
Compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A Nos. 63-201653 and 63-201654,
In one molecule described in JP-A-1-26842, SO ₂ −
A compound having X (X is as defined above) and an electron-withdrawing group,
In one molecule described in JP-A-63-271344, PO
A compound having an -X bond (X has the same meaning as above) and an electron-withdrawing group, a C-X 'bond (X' has the same meaning as X or -SO in one molecule described in JP-A-63-271341. _2- represents) and a compound having an electron-withdrawing group. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent No. 22.
Compounds (1) to (3) described in No. 0746A2,
(7) to (10), (12), (13), (15),
(23) to (26), (31), (32), (35),
(36), (40), (41), (44), (53)-
(59), (64), (70), Public Technical Report 87-619
No. 9 compounds (11) to (23) and the like.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524 and Japanese Patent Publication No. 48-39,165.
U.S. Pat. Nos. 3,443,940 and 4,47.
No. 4,867, No. 4,483,914 and the like.

A compound (DRR compound) that is reducible to a silver halide or an organic silver salt, and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are US Pat. Nos. 3,928,312 and 4,053,312.
No. 4,055,428, No. 4,336,32
2, JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, 51-104, 343,
RD17465, U.S. Pat. No. 3,725,062,
No. 3,728,113, No. 3,443,939
No. 58-116,537, 57-1798.
40, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626 in columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13),
(16)-(19), (28)-(30), (33)-
(35), (38) to (40) and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, No. 37
The compounds described in columns 39 to 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and general formula [L1], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, 54-58). Azo dyes used in the heat-development silver bleaching method of U.S. Pat.
5,957, Research Disclosure, 19
(April 1976 issue, pages 30-32, etc.), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617, etc.) and the like can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layers of the light-sensitive element 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, No. 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 or less, based on 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-5994
A dispersion method using a polymer described in No. 3 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, 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 element. Specific compounds preferably used are described in US Pat. No. 4,500,
No. 626, columns 51-52.

The dye fixing element has a dye fixing layer, and if necessary, auxiliary layers such as a protective layer, an anti-curl layer and an intermediate layer can be provided. In particular, it is useful to provide a protective layer when it is arranged in the outermost layer. One or more of the above layers may include hydrophilic thermal solvents, plasticizers, anti-fading agents, UV absorbers, slip agents, matting agents, antioxidants, dispersed vinyl to increase dimensional stability. A compound or the like may be included. Further, in a photographic element having no back layer as an anti-curl layer, a polymer dispersion having a low Tg is contained in the dye fixing element, the white reflective layer and / or the light-sensitive element to lower the elastic modulus of the photographic element. Is valid.

In the present invention, the dye fixing layer preferably contains a polymer mordant capable of fixing the mobile dye released by the development. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, or the like. Further, a polymer mordant containing a group of imidazole or a derivative thereof has high light fastness, and the curling effect of the water-soluble polymer containing an alkylene oxide group used in the present invention is remarkable and is preferably used.

Polymers containing vinyl monomer units having a tertiary amine group are described in JP-A-60-60643.
And JP-A-60-57836, and specific examples of the polymer containing a vinyl monomer unit having a tertiary imidazole group include JP-A-60-118834,
No. 60-122941, JP-A-62-244043.
No. 62-244036, U.S. Pat. No. 4,282,
No. 305, No. 4,115,124, No. 3,14
No. 8,061. Specific examples of the polymer containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101 and
093,041, 1,594,961, US Patents 4,124,386, 4,115,124.
No. 4,433,853, 4,450,22
4 and JP-A-48-228225. Other specific examples of the polymer containing a vinyl monomer unit having a quaternary ammonium salt include US Pat.
709,690, 3,898,088, 3,958,995, JP-A-60-57836, 60-60643, 60-122940, 60.
-122942 and 60-235134.

The molecular weight of the polymer mordant used in the present invention is preferably 1,000 to 1,000,000, and particularly 10,000 to 200,000. Such a polymer mordant is used in the mordant layer in the dye fixing element in combination with a hydrophilic colloid as a binder described later. The mixing ratio of the polymer mordant and the hydrophilic colloid and the coating amount of the polymer mordant are easily determined by those skilled in the art according to the amount of the dye to be mordant, the type and composition of the polymer mordant, and the image forming method to be applied. However, the mordant / hydrophilic colloid ratio is 20/80 to 80/20 (weight ratio), and the mordant coating amount is preferably about 0.2 to about 15 g / m ² , and particularly 0.5 to It is preferably used at 8 g / m ² .

The polymeric mordant can be used in combination with metal ions in the dye fixing element to increase the transfer density of the dye. This metal ion can be added to a mordant layer containing a mordant or a layer adjacent thereto (either on the side closer to the support carrying the mordant layer or on the side farther from the support). The metal ion used here is preferably colorless and stable to heat and light. Ie Cu
²⁺ , Zn ²⁺ , Ni ²⁺ , Pt ²⁺ , Pd ²⁺ , Co ³⁺ ions and other multivalent ions of a ring transfer metal are preferable, and Zn ^{2+ is} particularly preferable.
Is preferred. The metal ions in the form of ordinary water-soluble compounds, for example, be added in _{ZnSO 4, Zn (CH 3 CO} 2) 2, the amount added is suitably from about 0.01 to about 5 g / m ^2, preferably 0 0.1 to 1.5 g / m ² . A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, hydrophilic colloids which are specifically listed later are useful. The mordant layer containing the polymer mordant may contain various surfactants for the purpose of enhancing coatability.

The photographic elements of this invention contain bases and / or base precursors. The base and / or base precursor may be contained in any of the light-sensitive element, the white reflective layer (including the foaming layer) and the dye fixing element, but it is preferably contained in at least the white reflective layer. Examples of the base in the present invention include alkali metal, quaternary alkylammonium hydroxide, carbonate, bicarbonate, borate,
Inorganic bases such as secondary and tertiary phosphates, metaborates, etc .;
Aliphatic amines, aromatic amines, heterocyclic amines,
Examples thereof include organic bases such as amidines, cyclic amidines, guanidines, cyclic guanidines, and their carbonates, bicarbonates, borates, and second and third phosphates.

Examples of the base precursor in the present invention include the above-mentioned organic base precursors. The base precursor as used herein is one that releases a basic component by thermal decomposition or electrolysis. For example, salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, acetoacetic acid, α-sulfonylacetic acid and the organic bases, salts with 2-carboxycarboxamide described in US Pat. No. 4,088,496, etc. Can be mentioned. Other British Patent No. 99
The base precursors described in U.S. Pat. No. 8,945, U.S. Pat. No. 3,220,846, JP-A-50-22625 and the like can be used. The salt of the thermally decomposable organic acid and the organic base, the salt of 2-carboxycarboxamide described in U.S. Pat. No. 4,088,496, and the like function as a base generator and a foaming agent (foaming agent for the foam layer). Alternatively, it can also serve as a compound that generates gas by light heat).

Further, the following compounds can be mentioned as the compounds which generate a base by electrolysis. For example, electrolysis of various fatty acid salts can be mentioned as a representative method using electrolytic oxidation. By this reaction, carbonates of organic bases such as alkali metals, guanidines and amidines can be obtained very efficiently. As a method using electrolytic reduction, amines are produced by reduction of nitro and nitrone compounds, amines are produced by reduction of nitriles;
Examples include production of p-aminophenols, p-phenylenediamines, and hydrazines by reduction of nitro compounds, azo compounds, azoxy compounds and the like. p-
Aminophenols, p-phenylenediamines and hydrazines can be used not only as bases but also directly as color image-forming substances. Further, it is of course possible to use an alkaline component produced by electrolysis of water in the presence of various inorganic salts.

Further, as described in US Pat. No. 4,740,445, with a medium of metal ions and water constituting a sparingly soluble metal salt compound (for example, zinc oxide, basic zinc carbonate, calcium carbonate, etc.). A method of generating a water-soluble base by reacting a compound capable of complexing reaction (eg, guanidine picolinate) with the sparingly soluble metal salt compound can also be used. In this method, a dispersion of a sparingly soluble metal salt compound is contained in a light-sensitive element and a compound capable of complexing with the metal ion as a base precursor is contained in a dye-fixing element, and a base is generated during heat treatment. You can Hydrochloric acid and / or base precursor alone 2
A combination of two or more species can also be used. The amount of the base and / or base precursor used is 5 × 10 ^{−4 to} 5
× 10 ^-1 mol / m ² , preferably 2.5 × 10 ^-3 to 2.
It is in the range of 5 × 10 ^-2 mol / m ² .

Next, the white reflective layer will be described. The white reflective layer comprises at least a hydrophilic binder and a white pigment. Examples of the white pigment include calcium carbonate, titanium oxide,
Examples include talc, clay, kaolin and the like.

The white reflecting layer is a layer (foaming layer) which is transparent until the photographic element is exposed, but which contains a compound which decomposes by heating or photothermal treatment to generate gas to foam and whiten. May be. As the foaming agent used for such a foam layer, there are a pyrolysis foaming type and a photopyrolysis foaming type. When using a pyrolysis foam type, it may be foamed by heat before heat development, or may be foamed simultaneously with heat development,
Moreover, you may heat-foam after heat development. The photothermolysis foaming type is usually subjected to a foaming treatment by heating after heat development, simultaneously with irradiation with ultraviolet rays or by heating after irradiation.

As the thermal decomposition type foaming agent, an azo compound (eg ADCA: azodicarbonamide, AIBN: azobisisobutyronitrile etc.), a nitroso compound (eg DPT: N, N'-dinitrosopentamethylene tetramine etc.) , Sulfonyl hydrazide compounds (eg TH
S: p-toluenesulfonyl hydrazide, OBSH:
p, p'-oxybis (benzenesulfonyl hydrazide) and the like). Furthermore, as a thermal decomposition type foaming agent,
A decarboxylation type carboxylate type that also serves as a base precursor is preferably used. Specific examples thereof include the compounds described on pages 63 to 79 of Known Technology No. 5 (published on March 22, 1991, Aztec Co., Ltd.).
Examples of the photothermal decomposition foaming agent include diazo compounds, azide compounds, quinonediazide compounds and the like. Specifically, it is described on pages 6 to 8, pages 89 to 111, and pages 182 to 215 of "Basics of Photographic Engineering -Non-Salt Photographic Edition-" (edited by the Photographic Society of Japan, 1992, published by Corona Publishing Co., Ltd.). Compounds.

In order to control the foam size of the foam layer, it is effective to add an oil emulsion to the foam layer. The oil droplet size of the oil emulsion is preferably 1 μm or less, and particularly preferably 0.5 μm or less. The oil used for the oil emulsion may be liquid or fixed, but is preferably fixed oil having a melting point of 40 ° C to 200 ° C. Examples of the oil include high boiling point organic solvents (including solid oil) for dispersing a hydrophobic additive such as a dye-providing compound described below.

As the binder used in the foamed layer of the present invention, the binder used in the light-sensitive element and dye fixing element described later can be used, but the glass transition temperature is 30 to 2
A water-soluble polymer having a temperature of 00 ° C, particularly 40 to 150 ° C is more preferable. The foam layer has a glass transition temperature of 30 to
It is preferable to include an emulsion dispersion or latex of an oil-soluble polymer at 250 ° C, preferably 40 to 200 ° C, particularly preferably 50 to 150 ° C, because fine and uniform bubbles can be easily formed. The content of the oil-soluble polymer is preferably 10 to 300% by weight, more preferably 20 to 200% by weight of the water-soluble polymer. The film thickness of the foamed layer of the present invention is 0.2 to 50 μm, preferably 0.
It is 5 to 30 μm, and more preferably 1 to 10 μm.

In the case of a photographic element having a foaming layer containing a foaming agent which generates gas at a temperature below the heat development temperature, the foaming layer of the present invention foams at the same time as the heat development and becomes a white reflection layer.
Further, in the case of a photographic element having a foaming layer containing a foaming agent which generates gas at a temperature higher than the heat development temperature, heat development is performed first, and then heating is performed at a temperature higher than the heat development temperature for a short time to foam. The heating conditions in this case are 100 to 200.
1 to 30 seconds at ℃, preferably 1-2 at 130 to 180 ℃
0 seconds, more preferably 1 to 10 seconds at 140 to 160 ° C. The foam size of the foam layer of the present invention is 0.1 to 100 μm.
m, preferably 0.2 to 50 μm, particularly preferably 0.
It is 5 to 30 μm. If the foam size is too large, the thickness of the foam layer becomes uneven, so that the diffusivity of the dyes diffusing through the foam layer becomes different, resulting in uneven image density. Further, since the foaming size is too small, the light scattering property is lowered, so that the function as the white reflective layer cannot be fulfilled.

Next, the release layer will be described. The release layer contains
It is preferable to include a release agent. Examples of the release agent include solid substances such as polyethylene wax, amide wax, fine powder of silicone resin, fine powder of fluororesin, and wax-like substances: Fluorine-based, phosphate ester-based surfactants: paraffin-based, Conventionally known release agents such as silicone-based and fluorine-based oils can be used,
Silicone oil is particularly preferable. As the silicone oil, in addition to unmodified silicone oil, modified silicone oil such as carboxy-modified, amino-modified, epoxy-modified, polyether-modified and alkyl-modified can be used alone or in combination of two or more kinds. As an example, 6 of the technical data of "modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
The various modified silicone oils described on page 18B can be mentioned.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element, the white reflective layer and the dye fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives or cellulose derivatives, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic high molecular compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃
Homopolymers of vinyl monomers having M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, manufactured by Sumitomo Chemical Co., Ltd.) Sumika gel L-5H) is also used. These binders can be used in combination of two or more.

In the case of the present invention in which a small amount of water is supplied for thermal development, the use of the superabsorbent polymer makes it possible to quickly absorb water. Further, when a polymer having an OH group and / or a COOM (M is the same as above) group is used in the dye fixing layer, the intermediate layer and the protective layer thereof, and particularly in the protective layer, the dye may be separated from the dye fixing element after transfer. Can be prevented from being retransferred. Especially O
The effect becomes remarkable by using the H group-containing polymer in combination with boric acid or a salt thereof. Examples of the above-mentioned polymer having an OH group and / or COOM (M is the same as above) group include the above-mentioned superabsorbent polymer, polyvinyl alcohol, and polysaccharides (for example, dextran, pullulan, hydroxyethyl cell sauce, etc.). Can be mentioned. In the present invention, both the dye-fixing element and the light-sensitive element, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

Hardeners used in the constituent layers of photographic elements include US Pat. No. 4,678,739, column 41, JP-A-59-116655, JP-A-62-245261, and JP-A-6-245261.
Examples include hardeners described in No. 1-18942. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone 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).

In the present invention, an image formation accelerator can be used in the photographic element. The image formation 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 accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound,
It is classified into high boiling organic solvents (oils), thermal solvents, surfactants, compounds that interact with silver or silver ions, and the like.
However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For more details on these, see US Pat. No. 4,678,7.
No. 39, columns 38-40.

In the photographic element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to changes 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 to reduce the concentration of the base in the film to stop the development after proper development, or inhibits 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-62-253159 (31) to (3)
2) page.

The constituent layers of the photographic element (including the back layer) include various polymer latices for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Can be included. Specifically, JP-A Nos. 62-245258 and 62-13664.
Any of the polymer latexes described in No. 8 and No. 62-110066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used in the mordant layer, cracking of the mordant layer can be prevented.

High boiling organic solvents can be used as a plasticizer and a sliding agent in the constituent layers of the photographic element. Specifically, JP-A-62-253159, page (25), ibid.
No. 245253 and the like. Furthermore,
For the above purpose, 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. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical materials P1 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy modified silicone (trade name X-22-371).
0) etc. are effective. In addition, JP-A-62-215953
The silicone oils described in JP-A-63-46449 are also effective.

Optical brighteners may be used in the photographic elements of the invention, especially in the dye fixing elements. In particular, it is preferable that the dye-fixing element contains a fluorescent whitening agent or is supplied from the outside of the light-sensitive element. An example is K. Veenkatar
aman ed "The Chemistry of Sy"
“Neticic Dyes”, Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based compounds.
The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the constituent layers of the photographic element of the present invention, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463 and 6-62.
2-183457 and the like.

The constituent layers of the photographic element of the present invention may also contain an organic fluoro compound for the purpose of improving sliding property, antistatic property, improving releasability and the like. Typical examples of the organic fluoro compound include fluorine-containing surfactants and fluorine oils described in JP-B-57-9053, columns 8 to 17, JP-A-61-29444, JP-A-62-135826 and the like. The hydrophobic fluorine compound such as the oily fluorine compound or the fixed fluorine compound resin such as tetrafluoroethylene resin.

Matting agents can be used in the photographic elements of this invention. Matting agents such as silicon dioxide, polyolefins and polymethacrylates are disclosed in JP-A-61-8.
8256 (29) page, benzoguanamine resin beads, polycarbonate resin beads, AS
Resin beads and the like JP-A-63-274944 and 63-63
There are compounds described in -274952. In addition, the photographic element of the present invention may contain a thermal solvent, an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256 (26) to (32).
Page.

As the support for the photographic element of the present invention, one that can withstand the processing temperature is used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (for example, triacetyl cellulose) or those films containing pigment such as titanium oxide, film synthetic paper made from polypropion, synthetic resin pulp such as polyethylene, and natural pulp Mixed paper, yankee paper, baryta paper, coated paper (particularly cast coated paper), cloth, etc. that are made 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 (2
The supports described on pages 9) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on the light-sensitive element, for example, a method of directly photographing the air volume or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or a stretcher, 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 of image information, 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. 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. An image signal created by using a computer represented by Signal, CG and CAD can be used.

The heat development step of the present invention will be described. Although it depends on the constitution of the photographic element of the present invention, for example, when a thermal decomposition type base precursor is used, the following steps are included. After the imagewise exposure of the photographic element, the base precursor is decomposed by preheating with a heat block or a heat roller to generate a base, and then a small amount of water is applied and brought into contact with a heated inert liquid for thermal development. Spread. When the photographic element has a peeling layer as in the constitution (2), the photographic element is peeled off in a wet state before drying the photographic element or in a dry state after drying.
Further, in the case where the photographic element has a foam layer as in the constitution (2), it may be foamed by pre-heating, or may be foamed after being dried after thermal development.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic water-soluble solvent containing an inorganic alkali metal salt or an organic base. As the base, those described in the section of the image formation accelerator are used). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic water-soluble solvent can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used in the method of applying to a photographic element. The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the entire coating machine). A method for applying a solvent to a photographic element is described in, for example, JP-A-61-14724.
No. 4, page (26). Alternatively, the solvent may be contained in a microcapsule and previously incorporated in the light-sensitive element or the dye-fixing element or both of them.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive element or the dye-fixing element can also 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 the hydrophilic thermal solvent include ureas, pyridines, amides, sulfonamides, imides, alkenyls, oximes and other heterocycles. Specific examples of the hydrophilic thermal solvent and particularly preferred specific examples thereof include the compounds described on pages 149 to 158 of JP-A-58-42092. Further, as an example of the hydrophilic thermal solvent, US Pat. No. 3,347,675 is used.
No. 3,667,959, No. 3,438,776
No. 3,666,477, Research Disclosure (No. 17,643), JP-A-51-1952.
5, No. 53-24829, No. 53-60223,
58-1186640, 58-198038,
59-229556, 59-68730, 5
9-842236, 60-191251, 60
-232547, 60-142241, 61-
No. 52643, No. 62-785554, No. 62-42
No. 153, No. 62-44737, No. 63-53548.
No. 63-161446, JP-A No. 1-224751.
The thermal solvent described in each of the publications such as No. 2, No. 2-863 and the like can also be mentioned. In addition, in order to promote dye transfer,
The high boiling point organic solvent may be contained in the photosensitive element and / or the dye fixing element. The hydrophilic thermal solvent may be used alone or in combination of two or more kinds. The hydrophilic thermal solvent is contained in an amount of 10 to 10 which is the total coating film thickness excluding the hydrophilic thermal solvent in the foam layer, the light-sensitive element or the dye fixing element.
It can be used in the range of 300% by weight, preferably 20 to 200% by weight, particularly preferably 30 to 150% by weight.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Example 1 A method for preparing a dispersion of an electron transfer agent will be described.

10 g of the following electron transfer agent and 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant
g, 0.5 g of the following anionic surfactant was added to a 5% gelatin aqueous solution, and the mixture was pulverized with a mill for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.4 μm.

[0082]

Embedded image

Next, a method for preparing a dispersion of the dye trapping agent will be described.

The following polymer latex (solid content 13
%) 108 ml, the following surfactant 20 g, water 1232 ml
600 ml of a 5% aqueous solution of an anionic surfactant described below was added over 10 minutes while stirring the mixed solution. Using the ultrafiltration module, the dispersion thus prepared,
It was concentrated to 500 ml and desalted. Next, 1500 ml of water was added and the same operation was repeated once again to obtain 500 g of the dye trapping agent dispersion.

[0085]

Embedded image

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Cyan, magenta, yellow, and electron donor gelatin dispersions were prepared according to the formulations in Table A, respectively. That is, each oil phase component was heated and dissolved at about 60 ° C. to form a uniform solution, and this solution and an aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed.
Dispersed at 00 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0088]

[Table 1]

[0089]

[Chemical 3]

[0090]

[Chemical 4]

[0091]

[Chemical 5]

[0092]

[Chemical 6]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride)
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.), 20 parts of the solutions (I) and (II) in Table B were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) in Table B were further added simultaneously at the same flow rate for 25 minutes. Also (II
10 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1 g of gelatin in 105 ml of water, 67 mg of the following dye (a), 133 mg of the following dye (b), and the following dye (c) ) Containing 4 mg and kept at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0096]

[Chemical 7]

[0097]

[Table 2]

[0098]

Embedded image

[0099]

[Chemical 9]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] An aqueous solution of well-stirred gelatin (in 783 ml of water, 20 g of gelatin, 0.5 g of potassium bromide and 6 parts of sodium chloride).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.), 30 parts of the liquids (I) and (II) in Table C were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) in Table C were further added simultaneously at an equal flow rate for 15 minutes. Also (II
2 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (0.9 g of gelatin in 95 ml of water, 61 mg of the above dye (a), 121 mg of the above dye (b), and the above dye) (C) The solution containing 4 mg and kept at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0102]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide and 4 g of sodium chloride in 675 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 48 ° C.), the liquids (I) and (II) in Table D were simultaneously added to 10 parts.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table D were further added simultaneously at an equal flow rate for 20 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (3.0 g of gelatin in 120 ml of water and 300 mg of the following dye (d) and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0105]

[Table 4]

[0106]

[Chemical 10]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 675 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 55 ° C.), 20 parts of the liquids (I) and (II) in Table E are simultaneously added.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) shown in Table E were simultaneously added at an equal flow rate for 20 minutes. Also (I
II), 1 minute after the addition of the liquid (IV), an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 95 ml of water and 250 mg of the above-mentioned dye (d) and kept at 45 ° C.) was added together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.42 μm was obtained.

[0109]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 4 in 675 ml of water).
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 50 ° C.), the solutions (I) and (II) in Table F were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, the solutions (III) and (IV) in Table F were further added simultaneously at an equal flow rate for 32 minutes. Also (II
One minute after the addition of the solutions (I) and (IV) was completed, an aqueous solution of the dye (water 9
220 mg of the following dye (e) in 5 ml and 5 ml of methanol
And 110 mg of the following dye (f) and kept at 45 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene was added for optimum chemical sensitization at 68 ° C. Thus, a monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm
35 g were obtained.

[0112]

[Table 6]

[0113]

[Chemical 11]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 675 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 65 ° C.), the solution (I) and the solution (II) in Table G are simultaneously added to 10 times.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table G were added simultaneously at the same flow rate for 30 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of the dye (water 6
150 mg of the above dye (e) in 6 ml and 4 ml of methanol
And 75 mg of the above-mentioned dye (f) and kept at 60 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0116]

[Table 7]

Using the above, the light-sensitive element shown in Table H was simultaneously coated with the foam layer shown in Table I.

[0118]

[Table 8]

[0119]

[Table 9]

[0120]

[Table 10]

[0121]

[Chemical 12]

[0122]

[Chemical 13]

[0123]

[Table 11]

[0124]

Embedded image

A photographic element 100 was prepared by further coating a dye fixing element as shown in Table J on the above photographic element.

[0126]

[Table 12]

[0127]

[Chemical 15]

[0128]

Embedded image

In the photographic element 100 thus produced, the density of which continuously changes from the dye fixing element side Y,
After imagewise exposure through the wedges of M, C, and gray, it was heated at 150 ° C. for 4 seconds with a heat roller to simultaneously fire and generate a base. Next, add water to this with a rod bar 15
ml / m ² to swell the coating film of the photographic element, and to 85 ° C.
The sample was conveyed in the Fluorinert FC70 (manufactured by 3M Company) that had been heated to 2 and heated for 25 seconds. When the photographic element thus treated was dried and then observed from the dye-fixing element side, a uniform color image having excellent S / N and having no unevenness was formed.

Example 2 A back layer shown in Table K was coated on a 180 μm polyethylene terephthalate film, and then the dye-fixing element shown in Table L and a white reflective layer were simultaneously coated on the opposite surface thereof, and then Table M was used.
Photographic elements 200 were prepared by successively coating the photosensitive elements shown in FIG.

[0131]

[Table 13]

[0132]

[Table 14]

[0133]

[Table 15]

[0134]

[Table 16]

[0135]

[Table 17]

[0136]

[Chemical 17]

After the image of the photographic element 200 produced in this manner was image-processed from the back side, the photographic element 200 was heated with a heat roller for 15 minutes.
The base was generated by heating at 0 ° C. for 5 seconds. Next, 15 ml / m ^{2 of} water was applied to this with a rod bar to swell the coating film of the photographic element, and Fluorinert FC70 heated to 85 ° C.
The contents were conveyed and heated for 25 seconds. When the photographic element thus treated was dried and observed from the side of the base film, a uniform color image having no unevenness and excellent S / N was formed.

Example 3 A light-sensitive element having the constitution shown in Table N was prepared and designated as a light-sensitive element 101.

[0139]

[Table 18]

[0140]

[Table 19]

[0141]

[Table 20]

As the dye-fixing element, the layer structure shown in Table O was coated on a support having the structure shown in Table P to prepare dye-fixing element 101. However, the optical brightening agent (1) in the second layer was dissolved in the high-concentration bottom solvent (1) and ethyl acetate, culture-dispersed in a gelatin aqueous solution, and introduced into the same layer.

[0143]

[Table 21]

[0144]

[Table 22]

The light-sensitive element produced as described above was exposed by scanning an original image (a test chart in which yellow, magenta, cyan, and gray wedges having continuously changing densities are recorded) through a slit, and at 50 ° C. After immersing in water kept warm for about 2.5 seconds, squeeze it with a roller and immediately superimpose it so that the dye fixing element and the film surface come into contact with each other, and heat to 83 ° C. with an inert liquid Fluorinert FC.
70 was conveyed for 15 seconds and heated. Then, the light-sensitive element and the dye-fixing element were peeled off to obtain a color image corresponding to the original image on the dye-fixing element. The color image obtained in this way is
The image was uniform, had no unevenness, and had an excellent S / N ratio.

[0146]

According to the present invention, heat treatment of a heat-developable photographic element causes a sufficient heat-development reaction, and
A good image that is uniform and has no image unevenness can be obtained.
Further, no waste is generated, environmental protection and cost are excellent, and maintenance is easy.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 13, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0117

[Correction method] Change

[Correction content]

[0117] The photosensitive element shown in Table H using the above ones were simultaneously coated a foamed layer shown in Table I.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0123

[Correction method] Change

[Correction content]

[0123]

[Table 11]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0124

[Correction method] Change

[Correction content]

[0124]

Embedded image

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0125

[Correction method] Change

[Correction content]

[0125] coated with a dye-fixing element, such as shown in further Table J onto the photographic element, was created made the photographic element 100.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0137

[Correction method] Change

[Correction content]

The photographic element 200 thus produced was imagewise exposed from the back side, and then exposed to heat with a heat roller.
The base was generated by heating at 0 ° C. for 5 seconds. Then, 15 ml / m ^{2 of} water was applied to this with a rod bar to swell the coating film of the photographic element, and Fluorinert FC70 heated to 85 ° C.
The contents were conveyed and heated for 25 seconds. When the photographic element thus treated was dried and observed from the side of the base film, a uniform color image having no unevenness and excellent S / N was formed.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0142

[Correction method] Change

[Correction content]

As the dye-fixing element, the layer structure shown in Table O was coated on a support having the structure shown in Table P to prepare dye-fixing element 101. However, the optical brightener (1) in the second layer is a high boiling point solvent.
(1) and dissolved in ethyl acetate, is obtained by introducing the emulsifying dispersion to the same layer in a gelatin aqueous solution.

Claims (4)

[Claims] 1. A method for heat treatment of a heat-developable photographic element, which comprises subjecting a photographic element swollen with water or a processing solution to heat treatment by bringing it into contact with a heated inert liquid. 2. A photosensitive element containing on a support at least a photosensitive silver halide, a hydrophilic binder and a dye-donor compound which produces or releases a diffusible dye corresponding to or opposite to the exposure dose, and an image. Photographic element having at least two elements, a dye-fixing element, into which a diffusible dye produced or released by developing in the presence of a base and / or a base precursor is diffused and fixed after such exposure or simultaneously with imagewise exposure. A monosheet type heat characterized by heat-development and / or diffusion of the diffusible dye to fix it to a dye fixing element by bringing it into contact with a heated inert liquid after moistening with a small amount of water. Development and diffusion method of heat treatment of color photographic elements. 3. A photosensitive element containing on a support at least a photosensitive silver halide, a hydrophilic binder and a dye-donor compound which produces or releases a diffusible dye corresponding to or inversely to the exposure dose, and an image. A photographic element having at least two elements, a dye-fixing element, into which a diffusible dye produced or released by developing in the presence of a base and / or a base precursor is diffused and fixed after such exposure or simultaneously with imagewise exposure. A method for heat treatment of a monosheet type heat development diffusion type color photographic element, which comprises heating, after heating, a small amount of water to wet the photographic element and bringing it into contact with a heated inert liquid. 4. A light-sensitive element containing on a support at least a light-sensitive silver halide, a hydrophilic binder, and a dye-donor compound which produces or releases a diffusible dye corresponding to or opposite to the exposure dose, and / or Alternatively, after the imagewise exposure or at the same time as the imagewise exposure, water is applied to the dye fixing element to which the diffusible dye produced or released by developing in the presence of a base and / or a base precursor is diffused and fixed. A heat development transfer type color photographic element characterized by heat-development and / or transfer of the diffusible dye to fix it to a dye-fixing element by bringing them into contact with a heated inert liquid in a state where they are superposed on each other. Heat treatment method.