JP3138896B2 - Dye fixing element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye fixing element for a heat-developable color light-sensitive material.

[0002]

2. Description of the Related Art Many methods have been proposed for obtaining a color image (color image) by thermal development. For example,
A method of forming a color image by combining an oxidized form of a developing agent formed by reduction of silver halide with a coupler is disclosed in U.S. Pat. Nos. 3,531,286 and 3,761,
Nos. 270 and 4,021,240, Belgian Patent No. 8
02, 519, Research Disclosure Magazine (hereinafter abbreviated as RD) 13742, and the like. A method of forming a positive dye image by heat development by a silver dye bleaching method using silver halide is disclosed in U.S. Pat.
No. 5,957, RD14433, RD15227 and the like. Further, a method of forming or releasing an imagewise diffusible dye from a dye-donating compound with the heat development of silver halide and transferring the diffusible dye to a dye-fixing element having a mordant with a solvent such as water. A method of transferring to a dye-fixing element with a high-boiling organic solvent, a method of transferring to a dye-fixing element with a hydrophilic heat solvent incorporated in the dye-fixing element, the movable dye is heat-diffusible or sublimable, Have been proposed.

In this method, a negative dye image or a positive dye image can be obtained with respect to the original by changing the kind of the dye-donating compound to be used or the kind of the silver halide emulsion (US Pat. Patent 4,4
63,079, 4,474,867, 4,47
8,927, 4,507,380, 4,50
Nos. 0,626 and 4,483,914;
No. 149046, No. 58-149047, No. 59-1
No. 52440, No. 59-154445, No. 59-16
No. 5054, No. 59-180548, No. 59-168
No. 439, No. 59-174832, No. 59-1748
No. 33, No. 59-174834, No. 59-17483
No. 5, 62-65038, 61-23245,
European Patent Publication Nos. 210,660A2 and 220,746
A2 etc.).

Japanese Patent Application Laid-Open No. Sho 62-47639 describes that the use of dextran as a dye-fixing element is effective in preventing base precipitation.

[0005]

In the above-described image forming method, after the dye-donating element (also referred to as a "photosensitive element") and the dye-fixing element are heat-developed and transferred to form an image, the dye-fixing element is raised. So-called "color transfer" in which the dye moves and the image density decreases when the dye-fixing element is stored under moisture and the dye-fixing element portion on a white background is colored.
There was a problem.

(Object of the Invention) It is an object of the present invention to provide a dye-fixing element having less color transfer (especially during storage under high temperature and high humidity).

[0007]

As a result of intensive studies on the object of the present invention, it has been found that color transfer can be remarkably improved by including dextran having a large molecular weight in the upper layer of the dye fixing layer. Incidentally, Japanese Patent Application Laid-Open No. 62-47639
The effect of dextran to prevent precipitation is preferably contained in the dye-fixing layer. Therefore, an object of the present invention is to provide a dye-fixing element having a dye-fixing layer containing at least a mordant, a base and / or a base precursor on a support, and having a molecular weight of at least 300,000 to 3 above the dye-fixing layer.
The problem was solved by a dye-fixing element characterized by containing one million dextrans.

The particularly preferred dextran of the present invention has a molecular weight of 500,000 to 2,000,000. The addition amount is 0.01 to
2 g / m ^2, are suitable in particular 0.05 to 1 g / m ² approximately.
If the molecular weight is 2,000,000 or more, it is difficult to handle the solution due to high viscosity, which is not preferable in terms of production suitability.

The dye-fixing element of the present invention has at least a dye-fixing layer containing a mordant and an upper layer containing dextran. Here, the upper layer means a layer farther from the support than the dye fixing layer. Even if the dye-fixing element is in a form separately coated on a support separate from the photosensitive element,
It may be in the form of being coated on the same support as the photosensitive element. For the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white background reflection layer, see US Pat.
The relationship described in column 57 of 500,626 is also applicable to the present invention. In the present invention, a form in which the dye-fixing layer and the upper layer are provided on a support separate from the light-sensitive material is particularly preferable.
In this case, the structure is, in order from the support, a dye-fixing layer containing a mordant and an upper layer containing dextran. An undercoat layer may be provided between the support and the dye fixing layer. An intermediate layer may be provided between the dye fixing layer and the upper layer of the present invention.

As the mordant used in the dye fixing layer, those known in the field of photography can be used. Specific examples include columns 58 to 59 of U.S. Pat. No. 4,500,626, pages (32) to (41) of JP-A-61-88256, and JP-A-62-2.
And mordants described in JP-A-44043 and JP-A-62-244036.

The photographic element of the present invention can be in various embodiments using thermal transfer. Here, a photosensitive element having an image forming layer and a dye fixing element having an image receiving layer used in a heat-developable color light-sensitive material will be described in detail.

The light-sensitive element used in the present invention basically has a light-sensitive silver halide, a binder, and a dye-donating compound (which may also serve as a reducing agent as described later) on a support. Further, an organic metal salt oxidizing agent and the like can be contained as needed. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photosensitive 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 using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, 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 photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. 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 which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetradecahedron, a flat plate with a high aspect ratio, or any other. Specifically, U.S. Pat. Nos. 4,500,626, column 50, 4,628,021, and Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1)
978), and any of the silver halide emulsions described in JP-A-62-253159 can be used.

Although the silver halide emulsion may be used as it is after unripe, it is usually used after chemical sensitization. Known sulfur sensitization, reduction sensitization, noble metal sensitization, selenium sensitization, and the like can be used alone or in combination for the emulsions of photosensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. In addition, JP
Silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-113235;
The acetylene silver described in 1-249944 is also useful.
Two or more organic silver salts may be used in combination. The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. 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, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

As the binder for the constituent layers of the photosensitive element and the dye fixing element, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, a protein such as a gelatin derivative or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, and polyvinyl alcohol;
Examples include polyvinylpyrrolidone, acrylamide weight, and other synthetic high molecular compounds. Also, Japanese Patent Application Laid-Open
No. 245260, etc., the superabsorbent polymer,
-COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal)
Or a copolymer of the vinyl monomers with each other or another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.). These binders can be used in combination of two or more kinds.

When a system for performing thermal development by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to quickly absorb water. Further, when the superabsorbent polymer is used for the dye fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly preferably 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, those known in the field of photosensitive elements can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. Examples of the reducing agent used in the present invention include columns 49 to 50 of U.S. Pat. No. 4,500,626 and Nos. 30 to 3 of U.S. Pat. No. 4,483,914.
Column 1, No. 4,330,617, No. 4,590,152
And JP-A-60-140335, pp. (17)-(18), JP-A-57-40245, JP-A-56-138736, and JP-A-59-138736.
No. 178458, No. 59-53831, No. 59-1
No. 82449, No. 59-182450, No. 60-11
9555, 60-128436 to 60-12
No. 8439, No. 60-198540, No. 60-1
No. 81742, No. 61-259253, No. 62-24
Nos. 4044, 62-131253 to 62-13
Up to 1256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220,746 A2. Various combinations of reducing agents, such as those disclosed in U.S. 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 used, if necessary, to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusible and reducible dye-providing compounds described later. In the present invention, the reducing agent is added in an amount of 0.1 to 1 mol of silver.
001 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, silver can be used as an image forming substance. In addition, when silver ions are reduced to silver under high temperature conditions, they may contain a compound that generates or releases a mobile dye corresponding to this reaction or vice versa, that is, contains a dye-donating compound. it can. First, examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
Specific examples of color developers and couplers by THJames
The Theory of the Photographic Process "4th edition 29
Pp. 1-334 and 354-361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
Nos. 9047, 59-111148, 59-124
No. 399, No. 59-174835, No. 59-2315
No. 39, No. 59-231540, No. 60-2950
No. 60-2951, No. 60-14242, No. 6
Nos. 0-23474 and 60-66249.

As another example of the dye donating compound,
Compounds having a function of diffusing without releasing a diffusible dye in an image form can be mentioned. The compound of this type can be represented by the following general formula [LI] (Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group. , Y represents a simple bond or linking group, and Z represents a difference in diffusivity of the compound represented by (Dye-Y) _n -Z corresponding to or inversely corresponding to a photosensitive silver salt having an image-like latent image. Or a group having the property of releasing Dye and causing a difference in diffusivity between the released Dye and (Dye-Y) _n -Z, and n represents 1 or 2. , N is 2, two Dy
eY may be the same or different. General formula [LI]
Specific examples of the dye-donating compound represented by are the following compounds. In addition, the following ~
Is to form a diffusible dye image (positive dye image) in reverse correspondence to silver halide development, and is to form a diffusible dye image (negative dye image) in response to silver halide development.
Is formed.

Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and the like. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

US Pat. No. 4,559,290, EP 220,746 A2, US Pat. No. 4,783,
As described in JP-A-396, Publication No. 87-6199, etc., 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. Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379, JP-A-59-185333,
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in, for example, JP-A-57-84453, U.S. Pat.
-101649, 61-88257, RD240
No. 25 (1984), etc., compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-1984.
No. 142,530, U.S. Pat. Nos. 4,343,893 and 4,619,884, compounds which release a diffusible dye by cleavage of a single bond after reduction; U.S. Pat. Examples include a nitro compound which releases a diffusible dye after electron acceptance described in US Pat. No. 223 and the like, and a compound which releases a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like.

Further, as more preferable examples, European Patent No. 220,746A2, JP-A-87-6199,
U.S. Pat. No. 4,783,396, JP-A-63-201
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A Nos. 653 and 63-201654;
No. 42, a compound having an SO ₂ -X (X is as defined above) and an electron-withdrawing group in one molecule.
No. 1344, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule.
Compounds having a CX ′ bond (X ′ has the same meaning as X or —SO ₂ −) and an electron-withdrawing group in one molecule described in No. 271341 can be mentioned. Also, JP-A-1-161
Compounds which can be used without releasing a diffusible dye after cleavage by a π bond conjugated to an electron accepting group described in JP-A Nos. Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are described in European Patent No. 220,74.
Compounds (1) to (3), (7) to (10), (12), (13), and (1) described in US Pat. No. 6,783,396 or US Pat.
5), (23)-(26), (31), (32), (35), (36), (40), (4
1), (44), (53)-(59), (64), (70), Published Technical Report 87-6
199, compounds (11) to (23), and the like.

Compounds which have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specific examples include British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940, and 4,474,867.
No. 4,483,914 and the like. Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DR
R compound). This compound does not require the use of another reducing agent, but is preferable because it does not cause a problem of image contamination due to oxidized decomposition products of the reducing agent. A representative example is U.S. Pat.
8,312, 4,053,312, 4,05
Nos. 5,428 and 4,336,322,
Nos. 65839, 59-69839 and 53-381
9, No. 51-104343, RD17465, U.S. Pat. Nos. 3,725,062 and 3,728,113
No. 3,443,939 and JP-A-58-11653.
7, No. 57-179840, U.S. Pat.
0,626 and the like. As specific examples of the DRR compound, the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44 can be used. Among them, the compounds (1) to (3),
(10)-(13), (16)-(19), (28)-(30), (33)-(35), (3
8) to (40) and (42) to (64) are preferred. U.S. Pat.
The compounds described in 639,408, columns 37 to 39 are also useful. In addition, as the above-mentioned couplers and dye-donating compounds other than the general formula [LI], dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure, 1978)
May, pp. 54-58), azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat. No. 4,235,957,
Research Disclosure Magazine, April 1976,
30-32, etc.), leuco dyes (U.S. Pat.
5,565, 4,022,617) and the like can also be used.

Hydrophobic additives such as a dye-donating compound and a nondiffusible reducing agent can be introduced into a layer of a photosensitive element by a known method such as the method described in US Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-Open No. 59-83154
Nos. 59-178451 and 59-178452
Nos. 59-178453 and 59-178454
And high-boiling organic solvents described in JP-A-59-178455, JP-A-59-178457, and the like, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donating compound used.
It is as follows. Also, 1 cc or less per 1 g of binder,
Further, 0.5 cc or less, particularly 0.3 cc or less is appropriate.
A 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, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing a hydrophobic compound in a hydrophilic colloid,
Various surfactants can be used. For example, those mentioned as surfactants on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the photosensitive element. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the constituent layers of the photosensitive element and the dye-fixing element, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the photosensitive element and the dye-fixing element. Specific examples include (25) of JP-A-62-253159.
Page, pp. 62-245253, and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd., p.
2-33710) is effective. Further, Japanese Patent Application Laid-Open No. Sho 62-2
The silicone oils described in 15953 and 63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive element and the dye-fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), and JP-A-54-48535, 62-13
Nos. 6641 and 61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, 4,254,195, columns 3 to 8, JP-A-62-174741, and JP-A-62-174741. 61-88256 (27)
Pp. (29), 63-199248, JP-A-1-755
68 and 1-74272.

Examples of useful anti-fading agents are described in JP-A-62-21.
No. 5272, pages (125) to (137). An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be previously contained in the dye-fixing element,
The dye may be supplied to the dye fixing element from the outside such as a photosensitive element. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the photosensitive element and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive element. For example, K. Veenkataraman ed., "The Chemistry of Synthetic
Dyes ", Vol. V, Chapter 8, and JP-A-61-143752. More specific examples include 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.

US Pat. No. 4,678,739 No. 4 discloses a hardening agent used in a constituent layer of a photosensitive element or a dye fixing element.
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

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, improving releasability, improving slipperiness, preventing static charge, and accelerating development. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457. 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 static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as a fluorine oil or a solid fluorine compound resin such as an ethylene tetrafluoride resin. No.

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952. In addition, the constituent layers of the photosensitive element and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256.
Nos. (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the formation of a dye from a dye-providing substance or the decomposition of a dye or the release of a diffusible dye, and the photosensitive element layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. A specific example is disclosed in U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing element from the viewpoint of improving the storage stability of the photosensitive element. In addition to the above, EP 210,660, US Pat. No. 4,740,445
And combinations of compounds which are capable of forming a complex with metal ions constituting these hardly soluble metal compounds (referred to as complex forming compounds) described in
Compounds that generate a base by electrolysis described in 232451 can also be used as the base precursor.
In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

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

In the present invention, as the support for the photosensitive element and the dye fixing element, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

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

As a light source for recording an image on a photosensitive element,
As described above, light sources described in U.S. 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. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can express nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is given,
Lithium niobate, potassium dihydrogen phosphate (KDP),
Lithium iodate, inorganic compounds and typified BaB ₂ O _4, urea derivatives, nitropyridine -N- oxide derivatives such as nitroaniline derivatives, such as 3-methyl-4-nitropyridine -N- oxide (POM) , JP 6
Compounds described in 1-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the image information is
Image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), image signals obtained by dividing an original image into a large number of pixels such as a scanner, CG, CAD, etc. An image signal created by using a computer can be used.

The photosensitive element and / or the dye-fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of the dye. The transparent or opaque heating element in this case is described in JP-A-61-1.
No. 45544 can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., but development at about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. or higher to about 10 ° C. lower than the temperature in the heat development step.

Although the movement of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the heating temperature is preferably 50 ° C. or higher and 100 ° C. or lower. Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of formation accelerator are used)
Can be mentioned. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex forming compound may be contained in the solvent.

These solvents can be used by a method applied to the dye fixing element, the photosensitive element, or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film). As a method for applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (26)
There is a method described on the page. Further, the solvent can be used by being incorporated in a photosensitive element or a dye-fixing element or both in advance in a form such as enclosing a solvent in microcapsules.

In order to promote dye transfer, a system in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element.

As a heating method in the development and / or transfer step, a heating block, a plate, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far-infrared lamp heater, or the like is contacted. Or passing through a high temperature atmosphere. A pressure condition and a method of applying pressure when the photosensitive element and the dye fixing element are overlapped and brought into close contact with each other are described in JP-A-61-1.
No. 47244, page 27, can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
An apparatus described in No. 44 or the like is preferably used.

[0049]

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

Example 1 A dye-fixing element (1) was prepared by forming a dye-fixing material having the constitution of Table-B on the support (1) shown in Table-A.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

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[0054]

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[0055]

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[0056]

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The fluorescent whitening agent (1) and the stain inhibitor (1) in the second layer of Table-B consist of a surfactant (1) and a high boiling organic solvent (1).
And the preparation of this emulsion added as an emulsion using ethyl acetate. This emulsion was prepared by the following steps. 20 g of optical brightener (1), 60 g of stain inhibitor (1)
And 10 g of surfactant (1) and high boiling organic solvent (1) 6
The mixture was heated to 65 ° C. and dissolved in 50 g and 400 cc of ethyl acetate. 2,000 cc of a 15% aqueous gelatin solution
And at 10,000 rpm using a stirring emulsifier at 45 ° C.
The mixture was emulsified with stirring at 15 m for 15 minutes. Further, the dye-fixing elements (2) to (7) were prepared in the same manner as the dye-fixing element (1) except that the additives of the second, third, and fourth layers in Table-B were changed to Table-C. Was prepared.

[0058]

[Table 3]

Further, a photosensitive element having the structure shown in Table-D was prepared, and was designated as photosensitive element (1).

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

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[0063]

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[0064]

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[0065]

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The above light-sensitive element and dye-fixing element were processed using an image recording apparatus described in Japanese Patent Application No. 63-137104. That is, an original image (a test chart in which wedges of yellow, magenta, and cyan with continuously changing density are recorded) is scanned and exposed through a slit, and the photosensitive element is immersed in water kept at 40 ° C. and for 5 seconds. After that, squeezed with a roller, and then immediately superimposed so that the dye fixing element and the film surface were in contact with each other,
Using a heat roller adjusted to 80 ° C,
Heated for 5 seconds. Next, when the photosensitive element and the dye fixing element were peeled off, a clear color image corresponding to the original image was obtained on the dye fixing element.

Next, the coated surface of the highest density part (Dmax) and the lowest density part (Dmin) of the obtained image were overlapped and 1.7 kg /
After standing at 33 ° C. and 85% RH under a load of m ² for 8 hours, the density of the lowest density part was measured. The results are shown in Table-E.

[0068]

[Table 6]

[0069]

As can be seen from Table E, in the dye-fixing elements (5) to (7) in which a molecular weight of 300,000 to 3,000,000 dextran was added to the upper layer of the dye-fixing layer, color transfer under high temperature and high humidity was clearly observed. Improve.

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Claims (1)

(57) [Claims] 1. A dye-fixing element having a dye-fixing layer containing at least a mordant, a base and / or a base precursor on a support, wherein at least a dextran having a molecular weight of 300,000 to 3,000,000 is contained in a layer above the dye-fixing layer. Characteristic dye fixing element.