JPH06161070A - Dyestuff fixing element - Google Patents

Abstract

PURPOSE:To provide the dyestuff fixing element which does not generate coating fault and precipitation of additives by using a water-soluble epoxy hardener as a hardener to be used for the dyestuff fixing element. CONSTITUTION:The photosensitive element contg. at least a photosensitive silver halide, hydrophilic binder and dyestuff donative compd. which forms or releases diffusive dyestuff in correspondence or reverse correspondence to an exposure has the dyestuff fixing layer fixed with the diffusive dyestuff formed or released by development in the presence of a base and/or base precursor after or simultaneously with imagewise exposure. This dyestuff fixing layer and/or other layer is hardened by the water-soluble epoxy hardener. The water- soluble epoxy hardener to be used has at least >=10%, preferably >=20%, more preferably >=50% solubility in water. Further, the hardener which does not separate to two upper and lower layers even when after mixing at all ratios with water and allowing the mixture to stand still is more particularly preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye fixing material for diffusively transferring and fixing a dye from a photosensitive element containing a photosensitive silver halide.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotographic method and diazo photographic method in photographic characteristics such as sensitivity and gradation control. It is used. In recent years, a technique has been developed that can easily and quickly obtain an image by changing the image forming method of a light-sensitive material using silver halide from the conventional wet processing using a developing solution to dry processing such as heating. Has been done.

Many methods have been proposed for obtaining a color image (color image) by thermal development. For the method of forming a color image by combining an oxidant of a developing agent and a coupler, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, Belgian Patent No. 802,51 are described.
No. 9 and Research Disclosure, 1975 September 9
Monthly pages 31, 32, U.S. Pat. No. 4,021,240 and the like. In such a method, an image of reduced silver and a color image are simultaneously formed on the exposed portion for heat development, and thus the color image becomes turbid.

To remedy these drawbacks, heating causes an imagewise formation of or release of a mobile (diffusible) dye which is transferred by a solvent such as water to a dye-fixing element having a mordant. Method, a method of transferring to a dye fixing element with a high boiling point organic solvent, a method of transferring to a dye fixing element by a hydrophilic thermal solvent incorporated in the dye fixing element, the movable dye is heat diffusible or sublimable, A method of transferring to a dye receiving element such as a support has been proposed (US Pat. Nos. 4,463,079 and 4,474.
No. 867, No. 4,478, 927, No. 4,50
7,380, 4,500,626, 4,4
83,914; JP-A Nos. 58-149046 and 58.
-149047, 59-152440, 59-
154445, 59-165054, 59-1
80548, 59-168439, 59-17
4832, 59-174833, 59-174.
834 and 59-174835).

In the above-described image forming method, a dye fixing element having at least one dye fixing layer is used to receive and fix the diffusible dye. In the above-mentioned image forming method, since the image forming reaction usually does not occur unless it is on the alkaline side, a light-sensitive element and / or a dye-fixing element may contain a base and / or a base precursor, or may be subjected to heat development transfer processing. It needs to be supplied from the outside. However, it is not preferable to supply it from the outside during the heat development transfer process from the viewpoint of simplicity. Also,
When a large amount of a base or a base precursor is contained in the light-sensitive element and stored for a long period of time, the photographic property tends to change, and it is preferably contained in the dye-fixing element. Further, in the above image forming method, when the diffusible dye generated or released in the light-sensitive element is a dye having anionic property or high polarity, the dye-fixing layer constituting the dye-fixing element contains a polymer mordant described later. This is preferable in terms of water resistance, sharpness, hue and the like. As a polymer mordant, a tertiary amino group, especially imidazo-, is used from the viewpoint of light fastness.
Polymers having a diol group are preferably used.

Further, in the layer constituting the dye fixing element, a polymer having an OH group or / and a COOH group (or a salt thereof) is usually used in order to improve the film quality, the photographic property and the preservability of a raw or processed sample. -Is preferably used. In particular, when a base or a base precursor which is slightly water-soluble is contained in the dye fixing element, there is a problem that they precipitate out with time (powder blowing). As a method for solving them, there is dextran or pullulan. And the like are added. Furthermore, if the coated surfaces of the treated samples are superposed facing each other under high humidity, retransfer of the transferred color image (adhesion color transfer) is likely to occur, but as a method to solve this, a carboxyl group salt is used as a monomer unit. The polymer contained therein is used as the uppermost layer (protective layer).
On the other hand, when the heat development transfer process is performed in the presence of a small amount of water,
It is essential that these layers constituting the dye fixing element are hardened with a hardener.

[0007]

However, particularly when a polymer having an OH group and / or a COOH group (or a salt thereof) is used as the binder of the protective layer, the reactivity with the hardener is higher than that of the mordant. Since it is too low, there is a problem that the protective layer is not sufficiently hardened to perform the heat development transfer treatment in the presence of a small amount of water, and therefore the protective layer is not sufficiently cured. Therefore, performances such as scratch resistance, adhesion resistance, powder blowing resistance, and adhesion transfer color transfer are not always sufficient. Further, depending on the hardening agent used, there is a problem that coating unevenness is likely to occur. As a result of the analysis, it was found that one of the causes is that oil droplets of the hardener are generated in the layer to which the hardener is added in the coating and drying step. When the hardener has a low solubility in water, the hardener is solubilized and used by using an organic solvent compatible with water and / or a large amount of a surfactant. Therefore, it is considered that when the organic solvent evaporates and the content decreases in the coating and drying step, the hardener hardens to form oil droplets. or,
The use of large amounts of surfactant causes another type of coating failure, retransfer of the color image that occurs when the processed sample is stored face-to-face under high humidity, and under high humidity. A problem is that the glossiness tends to decrease when the heat development transfer process is performed.

Therefore, an object of the present invention is to provide a dye fixing element using a hardener which does not cause uneven coating failure. Another object of the present invention is to provide a dye-fixing element hardened by a hardening agent which has a suitable balance between the reactivity of the cross-linking agent, the mordant, and the binder, and does not cause the above problems. That is. Further, the object of the present invention is to improve film quality (for example, scratch resistance, glossiness, adhesion resistance, etc.), photographic property (for example, high density, white background, etc.), and storage stability (for example, dust resistance, light resistance, etc.). It is to provide an excellent dye fixing element.

[0009]

The above objects can be achieved by the present invention described below. That is, the present invention provides 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 corresponding to an exposure dose,
Dye fixing element having a dye fixing layer to which the diffusible dye produced or released by developing in the presence of a base and / or a base precursor is transferred and fixed after or simultaneously with imagewise exposure. In, the dye fixing layer and / or the other layer is achieved by a dye fixing element characterized by being hardened by a water-soluble epoxy hardener.

The water-soluble epoxy hardener used in the present invention is
At least 10% solubility in water, preferably 20
% Or more, more preferably 50% or more. Further, those which do not separate into upper and lower two phases even when mixed with water in all proportions and allowed to stand are particularly preferable. The water-soluble epoxy hardener used in the present invention may have any structure as long as the water-solubility satisfies the above conditions, but as a group which imparts water-solubility, an alkylene oxide group, particularly ethylene oxide is usually used. Group or propylene oxide group. The following may be mentioned as specific examples of the water-soluble epoxy hardener used in the present invention.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

[0013]

[Chemical 3]

[0014]

[Chemical 4]

The water-soluble epoxy hardener used in the present invention is
They may be used alone or in combination of two or more. The amount of the water-soluble epoxy hardener used in the present invention is 0.01 to 3 with respect to the polymer component to be hardened in all coating layers.
The range is 0% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight. Further, when the dye fixing element is composed of a coating layer having a multi-layer structure, it can be added to any layer, but it is preferably added to a layer other than the dye fixing layer. That is, it may be added to any one of the undercoat layer, the intermediate layer and the protective layer, or two or more layers thereof. Since the water-soluble epoxy hardener used in the present invention has high water solubility, even if it is added to a part of the layers, it diffuses into all layers in the coating and drying step, and all layers are hardened. The water-soluble epoxy hardener of the present invention may be used as an undiluted solution or may be mixed with water at an arbitrary ratio and used. The dye-fixing element of the present invention is placed in a stacking relationship with the light-sensitive element at least during transfer of the diffusible dye. That is, the dye-fixing element is placed in such a relationship that the dye-fixing layer-coated surface is in face-to-face contact with the photosensitive layer-coated surface of the photosensitive element at least during transfer of the diffusible dye. The dye-fixing element of the present invention may be coated on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the dye reflection layer are described in US Pat. No. 4,500,626, No. 57.
The relationships described in the column can be applied to the present application. In the present invention, the dye fixing element is preferably coated on a support separate from the light-sensitive element.

The dye-fixing element has a dye-fixing layer on a support, and if necessary, an auxiliary layer such as a protective layer, a peeling layer, an anti-curl layer and an undercoat layer can be provided.
In particular, it is useful to provide a protective layer. One or more of the above layers may include a hydrophilic thermal solvent, a plasticizer, an antifade agent,
A UV absorber, a slip agent, a matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, and the like may be included. Further, in a dye-fixing element having no back layer as a curl prevention layer, in order to prevent curling of the dye-fixing element, a dye-fixing layer containing a polymer dispersion having a low Tg is used. It is effective to reduce the elastic modulus.

In the present invention, the dye fixing layer preferably contains a polymer mordant capable of fixing the movable dye released by 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. A polymer containing a quaternary cation group causes aggregation when used in combination with a polymer containing an anionic group. Even if it is used in another layer, it will be aggregated when mixed in the drainage pipe at the time of production, which causes a problem in production and thus limits the hydrophilic polymer to be used. A polymer mordant having a tertiary amino group or a nitrogen-containing heterocyclic moiety does not have such a problem and can be preferably used. 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, Japanese Patent Application No. 61-87180,
61-87181, U.S. Pat. No. 4,282,305.
No. 4,115,124, No. 3,148,06
No. 1 and the like.

Specific examples of the polymer containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, 1,594,961 and US Patent No. 4,124,38
No. 6, No. 4,115,124, No. 4,273,8
53, 4,450,224, JP-A-48-2
No. 8,225, etc.

Other specific examples of the polymer containing a vinyl monomer unit having a quaternary ammonium salt include US Pat. Nos. 3,709,690 and 3,898,088.
No. 3,958,995, JP-A-60-5783.
No. 6, No. 60-60643, No. 60-122940
No. 60-122942 and No. 60-23513.
No. 4 and the like.

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 can be determined by those skilled in the art depending on the amount of the dye to be mordant, the kind and composition of the polymer mordant, and the image forming method to be applied. It can be easily determined, but the mordant / hydrophilic colloid ratio is 20/80 to 8
0/20 (weight ratio), the amount of mordant applied is about 0.2 to about 1
5 g / m ² are suitable, preferably used in inter alia 0.5 to 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 dye-fixing element of the present invention contains a water-soluble base and / or base precursor. Examples of the base in the present invention include alkali metals, quaternary alkylammonium hydroxides, carbonates, bicarbonates, borates, and secondary salts.
And inorganic bases such as tertiary phosphate and metaborate; organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines and the like Carbonates, bicarbonates, borates, secondary and tertiary phosphates and the like.

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.

Further, the following compounds may 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, the medium is metal ions and water constituting a sparingly soluble metal salt compound (eg 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 water-soluble compound capable of undergoing a complex-forming reaction with the metal ion as a base precursor is contained in a dye-fixing element. It is particularly effective in terms of storability of the light-sensitive element and the dye-fixing element over time, since a base can be generated when heat-treated in close contact.

The hydrochloric acid and / or the base precursor may be used alone or in combination of two or more kinds.
The amount of base and / or base precursor used is 5 x 1
0 ^{-4 to} 5 x 10 ^-1 mol / m ² , preferably 2.5 x 10 ^-3
The range is from 2.5 × 10 ^-2 mol / m ² .

The light-sensitive element used in combination with the dye-fixing element of the present invention includes those which are wet-processed at around room temperature,
Further, it may be heat-developed, but the latter system is preferred because the effect of the present invention is more remarkable when used in combination with the dye fixing element of the present invention. The light-sensitive element basically has a photosensitive silver halide, a dye-donor compound (which may also serve as a reducing agent as described later), and a binder on a support, and further, if necessary, an organic metal. A hydrochloric acid 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 sensitive to 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 photosensitive element can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. The silver halide 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 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. Particle size is 0.1
˜2 μ, particularly 0.2 to 1.5 μ is preferable. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, tabular with a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, US Pat.
8,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1978), JP-A-6
Any of the silver halide emulsions described in JP-A-2-253159 can be used.

The silver halide emulsion may be used as it is without being post-ripened, but it 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. Along with the sensitizing dye, a dye having no spectral sensitizing effect by 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 and Japanese Patent Application No. 61-226294).

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.

When the dye-fixing element of the present invention is used in a heat developing system, an organic metal salt can be used as an oxidant together with the photosensitive silver halide in the light-sensitive element. 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 agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. Also, JP-A-60-11323
No. 5, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-2490.
The acetylene silver described in No. 44 is also useful. Organic silver salt is 2
You may use together 1 or more types. 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 US Pat. No. 4,500,626, columns 49 to 50, and US Pat. No. 4,483,914, columns 30 to 30.
Column 31, Id. 4,330,617, Id. 4,590,
No. 152, (17) to (18) of JP-A-60-140335.
Pp. 57-40245, 56-138736,
59-178458, 59-53831, 5
9-182449, 59-182450, 60
-119555, 60-128436 to 60
-128439, 60-198540, 6
0-181742, 61-259253, 62
-2444044, 62-131253 to 62
-131256, European Patent 220,746A2
No. 78 to 96, etc., 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 added, if necessary, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors 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 electron transfer agent or its precursor 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 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 that 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 mobile dye in response to the exposure dose 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 can be found in James, "The Theory of the Photographic Process," 4th Edition (TH
James "The Theory of the Photographic Process") 2
91-334 pages, and 354-361 pages, JP-A-58
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
24399, 59-174835, and 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249 and the like.

As another example of the dye-donating compound, a compound having a function of releasing or diffusing the 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 short-wavelength dye group or dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) _n -Z, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility from _n- Z, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. Good.

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 (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image). U.S. Pat. Nos. 3,134,764 and 3,36
No. 2,819, No. 3,597,200, No. 3,5
44,545, No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. 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 also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like. U.S. Pat. No. 4,559,290, European Patent No. 22
As described in No. 0,746A2, Kokai Giho 87-6199, and the like, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used. An example is U.S. Pat. No. 4,139,38.
9, No. 4,139,379, JP-A-59-185.
333, 57-84453, etc., compounds that release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107,
JP-A-59-101649, JP-A-61-88257,
A compound described in RD24025 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-142530, US Patent No. 4,343,89
Nos. 3,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, electrons described in US Pat. No. 4,450,223, etc. Examples thereof include a nitro compound that releases a diffusible dye after accepting it, and a compound that releases a diffusible dye after accepting an electron described in US Pat. No. 4,609,610 and the like. Further, as a more preferable one, European Patent No. 22
No. 0,746A2, Kokai Giho No. 87-6199, Japanese Patent Application No. 62-34953, No. 62-34954, etc., and an N—X bond (X represents an oxygen, sulfur or nitrogen atom) in one molecule. ) And a compound having an electron-withdrawing group, Japanese Patent Application No.
No. 106885, SO ₂ —X (X
Is the same as the above) and a compound having an electron-withdrawing group, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106895.
C-in one molecule described in Japanese Patent Application No. 62-106887.
X 'bond (X' is X as defined either or -SO ₂ - represents a)
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 EP 220,74.
Compounds (1) to (3), (7) to (10) described in 6A2,
(12), (13), (15), (23) to (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (59), (64), (70), compounds (11) to (23) of JP-A-87-6199. . 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 oxidized form of a reducing agent. Specifically, British Patent No. 1,33
0,524, Japanese Patent Publication No. 48-39,165, U.S. Pat. Nos. 3,443,940 and 4,474,867,
No. 4,483,914 and the like. A compound (DRR compound) that is reducing to a silver halide or an organic silver salt, and releases a diffusible dye when reducing a partner. 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, 4,053,312, 4,055,428, and 4,336,322.
JP-A-59-65839, JP-A-59-69839, JP-A-53-3819, JP-A-51-104,343 and RD1.
7465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116,537, 57-179840.
And U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13), (16) to (19), (2
8) to (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, Nos. 37-3
The compounds described in column 9 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 antidiffusive reducing agents can be incorporated into the layers of the light-sensitive element by known methods such as those 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 point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donor compound used.
It is the following. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder. The dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 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, JP-A-59
The surfactants listed on pages (37) to (38) of 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. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element 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 for example, gelatin, a protein such as gelatin derivative, or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, JP-A-62-1
No. 245260 and the like, a superabsorbent polymer, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymerization of the vinyl monomers with each other or with other vinyl monomers. Combined (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Further, a polymer having an OH group and / or a COOM (M is the same as above) group is used as a dye fixing layer, an intermediate layer and a protective layer thereof.
Among other things, when used in a protective layer, it can prevent the dye from retransferring from the dye-fixing element to another after transfer. In particular, the effect of the polymer having an OH group becomes remarkable by using it together with boric acid or its salt.
Examples of the polymer having the above 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, hydroxyethylcelso-). Etc.) and the like.

In the present invention, the coating amount of the binder for both the dye fixing element and the light-sensitive element 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 the light-sensitive element 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 light-sensitive element and / or the dye fixing 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, 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 accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40.

The light-sensitive element and / or the dye-fixing element of the present invention have the following properties with respect to fluctuations in processing temperature and processing time during development.
Various development terminators can be used for the purpose of always obtaining a constant image. 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-62-253
159 (31)-(32).

The constituent layer (including the back layer) of the light-sensitive element or the dye-fixing element is used 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 lower) is used in the mordant layer, cracking of the mordant layer can be prevented.

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. Specifically, (25) of JP-A-62-253159
Page, No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in "Modified Silicone Oil" technical data P1-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. The silicone oils described in JP-A Nos. 62-215953 and 62-23687 are also effective.

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 brightening agent in the dye fixing element or supply it from the outside such as a light sensitive element. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. 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, antistatic property, 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, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be 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.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further from polypropion etc. The film method synthetic paper to be made, a mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), cloth and the like are used. They are,
It 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-62-2531
The support described in No. 59, pages 29 to 31 can be used. On the surface of these supports a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a photosensitive element, for example, 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 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 heating temperature in the heat development step varies depending on the film pH adjusted by a base or a base precursor, but it can be developed at about 25 ° C. to about 250 ° C., but is 50 ° C.
-200 degreeC is preferable and 70-180 degreeC is especially useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. Although the transfer of the dye occurs only by heat, a solvent may be used to accelerate the transfer of the dye. Further, as described in detail in JP-A-59-218443, 61-238056, etc., a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also possible. It is useful. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, if the solvent is water, 5
It is preferably 0 ° C or higher and 100 ° C or lower.

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 by a method of applying them to the dye fixing element, the photosensitive element or both. 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 total coating film). As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-61
No. 147244, 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.

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, alkenyls, oximes and other heterocycles. Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater is contacted. It may be allowed to pass through, or may be transmitted through a high temperature atmosphere. Alternatively, a resistance heating volume may be provided in the light-sensitive element or the dye fixing element, and electricity may be supplied to the resistance heating volume for heating. As the heat generation volume, those described in JP-A-61-145544 can be used. A method for applying pressure and a pressure condition when the light-sensitive element and the dye-fixing element are superposed on each other and brought into close contact with each other are described in JP-A-61-61
The method described on page 147244 (27) can be applied.

Any of the known heat developing apparatus can be used to process the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used. The present invention will be further described below with reference to Examples.
The present invention is not limited to these.

[0067]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

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 a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. 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.

10 g of the following electron transfer agent, 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 0.35 μm.

[0072]

[Chemical 5]

[0073]

[Chemical 6]

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.

[0076]

[Chemical 7]

[0077]

[Chemical 8]

[0078]

[Chemical 9]

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

Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. 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, mixed by stirring, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Add to this,
Stir to obtain a uniform dispersion.

[0081]

[Table 1]

[0082]

[Chemical 10]

[0083]

[Chemical 11]

[0084]

[Chemical 12]

[0085]

[Chemical 13]

[0086]

[Chemical 14]

[0087]

[Chemical 15]

[0088]

[Chemical 16]

[0089]

[Chemical 17]

[0090]

[Chemical 18]

[0091]

[Chemical 19]

[0092]

[Chemical 20]

[0093]

[Chemical 21]

[0094]

[Chemical formula 22]

[0095]

[Chemical formula 23]

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

Light-Sensitive Silver Halide Emulsion (1) [For Red-Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 500 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.) at the same time as solutions (I) and (II) in Table 2
Added at equal flow rate for 1 minute. After 6 minutes, solution (III) and solution (IV) in Table 2 were further added simultaneously at an equal 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, 70 mg of the following dye (a), 139 mg of the following dye (b), and the following dye (c) ) Containing 5 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 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (2) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0099]

[Chemical formula 24]

[0100]

[Table 2]

[0101]

[Chemical 25]

[0102]

[Chemical formula 26]

[0103]

[Chemical 27]

Photosensitive Silver Halide Emulsion (2) [For Red Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 0.5 g of potassium bromide and 6 g of sodium chloride in 800 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.) at the same time as solution (I) and solution (II) in Table 3
Added at equal flow rate for 1 minute. After 5 minutes, the solutions (III) and (IV) in Table 3 were further added simultaneously at an equal flow rate for 15 minutes. Also (II
Two minutes after the start of addition of solutions I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1.1 g of gelatin in 95 ml of water, 76 mg of the following dye (a), 150 mg of the following dye (b), and the following dye) (C) 5 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 pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0106]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 4 parts of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 47 ° C.) were added simultaneously with the solutions (I) and (II) in Table 4 at the same flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 32 minutes. Also (II
1 minute after the addition of the solutions I) and (IV), an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 100 ml of water and 250 mg of the following dye (d) and kept at 45 ° C.) was added together. Was added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0109]

[Table 4]

[0110]

[Chemical 28]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and kept at 60 ° C.) at the same time as solution (I) and solution (II) in Table 5
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table 5 were further added simultaneously at an equal flow rate for 20 minutes. One minute after the addition of the liquids (III) and (IV) was completed, an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 75 ml of water and 180 mg of the following dye (d) and kept at 45 ° C.) was packaged together. And added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0113]

[Table 5]

Light-Sensitive Silver Halide Emulsion (5) [For Blue-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 5 in 690 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 51 ° C.) were added simultaneously with the solutions (I) and (II) in Table 6 at the same flow rate for 8 minutes. After 10 minutes, the solutions (III) and (IV) shown in Table 6 were further added simultaneously at an equal flow rate for 32 minutes. Also (II
One minute after the addition of solutions I) and (IV) was completed, an aqueous solution of dye (water 95
The following dye (e) (235 mg) and the following dye (f) (120 mg) were added to 100 ml of methanol and 5 ml of methanol and the mixture was kept at 45 ° C.).

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0116]

[Table 6]

[0117]

[Chemical 29]

[0118]

[Chemical 30]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 63 ° C.) at the same time as solution (I) and solution (II) in Table 7 at the same time.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table 7 were added simultaneously at the same flow rate for 30 minutes. One minute after the addition of the solutions (III) and (IV), the dye (e) 155 was added to an aqueous solution of dye (66 ml of water and 4 ml of methanol).
mg and the above dye (f) (78 mg) 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 pH to 6.0 and pAg to 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0121]

[Table 7]

A photosensitive material 101 shown in Table 8 was prepared using the above.

[0123]

[Table 8]

[0124]

[Table 9]

[0125]

[Table 10]

[0126]

[Chemical 31]

[0127]

[Chemical 32]

[0128]

[Chemical 33]

[0129]

[Chemical 34]

[0130]

[Chemical 35]

[0131]

[Chemical 36]

[0132]

[Chemical 37]

As a dye-fixing element, a dye-fixing element 101 was prepared by coating four layers of the layer structure shown in Table 11 simultaneously on a support having the structure shown in Table 12 at a coating speed of 120 m / min. However, the first layer and the third layer were prepared by the method described below with the formulation of the coating solution having the same composition. Optical brightener in the second layer (1)
Is dissolved in the high boiling point solvent (1) and ethyl acetate, emulsified and dispersed in a gelatin aqueous solution, and introduced into the same layer. Preparation of coating liquid for first and second layers: water / methanol (3
0/70: volume ratio) 600 ml and 2 of surfactant (3)
200 ml of 0% aqueous solution is mixed, and hardener (1) 2
The hardener (1) was solubilized by adding 00 g to prepare a 20% solution of the hardener (1). To 100 parts by weight of a 10% gelatin aqueous solution, 188 parts by weight of water, 30 parts by weight of a 20% solution of the hardener (1) prepared as described above and 15 parts by weight of a 5% aqueous solution of the water-soluble polymer (1) were added. To prepare coating solutions for the first layer and the second layer.

[0134]

[Table 11]

[0135]

[Table 12]

[0136]

[Chemical 38]

[0137]

[Chemical Formula 39]

Dye-fixing elements 02 and 03 were prepared in exactly the same manner as in the above dye-fixing element 01, except that hardeners (2) and (3) were used in equivalent amounts instead of the hardener (1). Next, in the above dye fixing element 01, the same as the dye fixing element 01 except that the hardener solution (equal equivalent) prepared as follows is used instead of the 20% solution of the hardener (1) prepared as described above. To prepare dye fixing elements 04 to 10. Hardener solution of dye fixing element 04: 20% of hardener (1)
% Methanol solution Hardener solution of dye fixing element 05: 20% of hardener (2)
% Methanol solution Hardener solution of dye fixing element 06: 20% of hardener (3)
% Methanol solution Hardener solution of dye fixing element 07: 20% of hardener (4)
% Aqueous solution Hardener solution of dye fixing element 08: Hardener H-1 (n = 2)
20% aqueous solution of Dye-fixing element 09 Hardener solution: Hardener H-2 20
% Aqueous solution Hardener solution of dye fixing element 10: Hardener H-3 (n = 1)
20% aqueous solution

[0139]

[Chemical 40]

Further, in the above dye-fixing element 08, dye-fixing element 11 was prepared in the same manner except that alkali-treated gelatin was used in place of water-soluble polymer (1) and carrageenan used in the fourth layer (protective layer). did. The dye-fixing element produced as described above was evaluated by carrying out the following tests, and the results are shown in Table 13. The image exposure and heat development transfer processing were carried out using the image recording apparatus described in Japanese Patent Application No. 63-137104. That is, an original image (a test chart in which yellow, magenta, cyan, and gray wedges having continuously changing densities are recorded) is scan-exposed through a slit, and the photosensitive element is exposed to about 2 degrees in water kept at 50 ° C. After soaking for 5 seconds, it was squeezed with a roller and immediately thereafter, superposed so that the dye fixing element and the film surface were in contact with each other, and heated for 15 seconds using a heat roller adjusted so that the water-absorbed film surface was 80 ° C. 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.

Evaluation of the above dye-fixing material Coating unevenness failure: Raw sample and processed print sample
Evaluation of unevenness ○: No unevenness △: Small but unevenness ×; There is unevenness Gloss: 45 ° incidence Adhesion resistance: Dye fixing element at 25 ° C. 80% RH, 3:00
After humidity control, the front and back are overlaid and 200g /
cm² Apply a load and peel at 25 ° C 80% RH for 3 days,
The above exposure and heat development transfer processing were performed. The obtained picture
The unevenness that was thought to be caused by adhesion on the image was evaluated. ◯: No unevenness Δ: Small but unevenly ×: Unevenness Photographic properties: maximum density (Dmax) of the obtained image and
The minimum density (Dmin) is the Macbeth reflection density diameter (RD41
5) was used. Yellow, magenta, cyan
Since a similar tendency was shown relatively, Table 13 shows magenta.
Data (green filter) only. Dust resistance: Raw sample of dye fixing element at 5 ° C 100
Storage at% RH for 1 week and observe the surface dusting condition for evaluation
did.  ○: No dust blowing △: Small but dust blowing ×: There was dust blowing Adhesive color transfer: Treated dye fixing element (black part and white part)
35 ℃, 80% RH, 1 day humidity control, and face the dye-fixing layer coated surface
Overlaid on each other 200g / cm² Apply the load of
It was stored at 35 ° C. and 80% RH for 3 days. Peel off both, black
The degree of retransfer of the color image from the image to the white area was evaluated. ○: No color transfer △: Some color transfer ×: Color transfer

[0142]

[Table 13]

As is clear from the results of Table 13, the dye fixing elements 08 to 010 of the present invention using the highly water-soluble epoxy hardener do not cause uneven coating, adhesion, dusting, etc.
The glossiness was high, and a high density white image was obtained.
Further, a polymer containing at least an OH group and / or a COOM (M is hydrogen or an alkali metal) group as a monomer component for improving adhesion color transfer [water-soluble polymer (1)]
Even with the use of, the use of the highly water-soluble hardener did not show uneven coating defects and deterioration of film quality (for example, scratch resistance, gloss, and adhesion resistance).

[0144]

EFFECT OF THE INVENTION By using a water-soluble epoxy hardener as a hardener used for the dye fixing element, a hardener having low water solubility can be mixed with a surfactant and / or a water-miscible organic solvent. The problems of coating unevenness, deterioration of film quality (for example, scratch resistance, glossiness, and adhesion resistance), reduction of transfer density, and powder blowing failure, which are observed when used after being solubilized, are improved. Furthermore, at least an OH group or / and a CO for improving adhesion color transfer.
Even in a dye fixing element containing a polymer containing an OM (M is hydrogen or an alkali metal) group as a monomer component in the dye fixing layer, the intermediate layer or the protective layer, particularly the protective layer, the film is sufficiently hardened and the film quality is deteriorated. And no powder blow failure is seen.

Claims (3)

[Claims] 1. 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 in response to or in inverse response to exposure dose is imaged. Dye-fixing element having a dye-fixing layer on which a diffusible dye produced or released by developing in the presence of a base and / or a base precursor is transferred and fixed after a uniform exposure or simultaneously with an imagewise exposure. A dye fixing element, wherein the dye fixing layer and / or the other layer is hardened with a water-soluble epoxy hardener. 2. A photosensitive element comprising on a support at least a photosensitive silver halide, a hydrophilic binder and a dye-donor compound which produces or releases a diffusible dye in response to or in response to exposure dose is imaged. Dye-fixing element having a dye-fixing layer to which the diffusible dye produced or released by developing in the presence of a base and / or a base precursor is transferred and fixed after continuous exposure or simultaneously with imagewise exposure. The dye fixing layer and / or the other layer contains a water-soluble polymer having a monomer containing a hydroxy group, a carboxyl group and / or a salt thereof as at least one constituent unit, and the dye fixing layer and / or Alternatively, the dye fixing element is characterized in that the other layer is hardened with a water-soluble epoxy hardener. 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 is imaged. Dye-fixing element having a dye-fixing layer to which the diffusible dye produced or released by developing in the presence of a base and / or a base precursor is transferred and fixed after continuous exposure or simultaneously with imagewise exposure. The outermost layer contains a water-soluble polymer having a monomer containing a hydroxy group, a carboxyl group and / or a salt thereof as at least one constituent unit, and the dye fixing layer and / or the other layer is water-soluble. A dye fixing element characterized by being hardened by the epoxy hardener of.