JP2896449B2 - 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 fixing and retaining a diffusible dye in a color diffusion transfer type photographic material. More specifically, the present invention relates to a dye-fixing element excellent in light fastness of an obtained image. About the element.

[0002]

BACKGROUND OF THE INVENTION The dye-fixing element of the present invention is used as an image-receiving material for fixing a dye formed or released as a result of development in a dye diffusion transfer type photographic material. This image forming system is roughly classified into a so-called wet color diffusion transfer system in which development is performed using a processing solution at around room temperature, and a thermal development diffusion transfer system in which development is performed at a temperature higher than room temperature. Both can be used as a suitable image receiving material. Both types are common to major materials such as dye-donating compounds and mordants, and there are many common problems, so the thermal development diffusion transfer method will be described in detail,
Except for parts unique to thermal development such as an organic silver salt and a developing method, the present invention can be applied commonly to the wet color diffusion transfer method.

In photographic materials of the dye diffusion transfer system,
Mordants have been used to fix the diffuse dye on the dye-fixing element. U.S. Pat. No. 3,898,088
Nos. 3,958,995, 4,131,469
No., West German Published Application No. 2,941,818;
Nos. 30328 and 56-17352 disclose such mordants.

When a dye-fixing element is manufactured using these mordants, there is a disadvantage that the mordant having a higher mordant power has a lower light fastness of the mordant dye. If the mordant power is reduced in order to increase the light fastness of the dye, problems such as a decrease in sharpness and a decrease in the maximum density arise. No mordant that satisfies both light fastness and mordant power has been developed so far.

The present inventors have conducted intensive studies and found that the higher the density of mordant dyes and the more the dyes exist on the surface of the dye fixing element, the faster the color fading of the dyes becomes. In order to suppress this reaction, a method of fixing the dye to a portion farther from the surface of the dye fixing element can be considered. However, if the mordant layer is placed away from the surface of the dye-fixing element for this purpose, there are problems such as an increase in dye transfer time and a decrease in the maximum density. Also, lowering the mordant power to uniformly mordant dye the mordant layer, the sharpness of the image deteriorates, lowering the density of the mordant increases the coating cost due to the increase in the thickness of the mordant layer, worsening curl, Increased transfer time,
There are problems such as a decrease in the maximum concentration.

[0006] Japanese Patent Application Laid-Open No.
No. 1-252551. This patent is similar to the present invention in that the mordant layer has two layers and two mordants having different mordant powers are used. However, there is no particular restriction on the positional relationship between the mordant layer having each mordant and the dye fixing element,
As a preferred positional relationship, it is better to dispose a mordant having a strong mordant power in the mordant layer far from the support. In the present invention, the positional relationship between two or more mordant layers and the support is important, and it can be considered that this is a selected invention of the patent.

[0007]

It is therefore an object of the present invention to provide a dye-fixing element having a high maximum density and low photobleaching of the mordant dye.

[0008]

The object of the present invention has been achieved by the following dye-fixing element. That is, in a dye-fixing element used in a photographic method of forming an image by diffusion-transferring a dye, the dye-fixing element has at least two or more mordant layers on a support, and a mordant layer closer to the support is preferably used. A dye-fixing element characterized by a high mordant density; and a dye-fixing element used in a photographic method for forming an image by diffusion transfer of a dye, wherein the dye-fixing element has at least two mordant layers on a support. And a mordant layer closer to the support contains a mordant having a higher mordant power.

Hereinafter, the present invention will be described in detail. The dye-fixing element of the present invention has at least two layers containing a mordant on a support. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in US Pat. No. 4,500,
No. 626, columns 58 to 59 and JP-A-61-88256, pages (32) to (41), mordants described in JP-A-62-2.
Nos. 44043 and 62-244036. Also, U.S. Pat.
No. 079, may be used. In each mordant layer of the present invention, these mordants may be used alone, or a mixture of a plurality of mordants, a copolymer, and a graft polymer as described in JP-B-54-19781 can also be used. It is. Further, these mordants may be polymerized with photographically useful agents described below.

The preferred density of the mordant used in the dye-fixing element of the present invention depends on the strength of the mordant, the molecular weight of the part providing the mordant, and the binder used.
It is 0.001 mmol / g or more and 40 mmol / g or less. Here, the density of the mordant refers to the number of moles of a portion that gives dye fixing ability and is contained per unit weight of all polymers contained in the same mordant layer.

In the present invention, "a mordant having a strong mordant power" means a mordant containing a portion imparting an equimolar dye-fixing ability on a support and diffusing and transferring the dye in an actual use form. A mordant that gives a high maximum concentration.

In the present invention, the phrase "the mordant layer closer to the support contains a mordant having a higher mordant power" means that the dye-fixing element of the present invention to which the dye has been transferred is placed in an environment of 80 ° C. and 70% RH.
After leaving for a day, a thin section was cut out, and the cross section was observed with an optical microscope, which means that the mordant layer closer to the support had a higher dye concentration. When performing this test, it is necessary to use a dye that diffuses from a photosensitive element that is actually used in combination with the dye-fixing element of the present invention.

When a graft polymer is used as a mordant, in addition to the quantitative ratio of the polymer serving as the backbone and the repeating unit providing the dye-fixing ability, the degree of polymerization of the repeating unit providing the dye-fixing ability can be changed. The amount of dyeing can be changed.

The preferred amount of the mordant used in the dye-fixing element of the present invention varies depending on the strength of the mordant and the number of mordants used. / M ² or more. More preferably, it is 10 mmol / m ² or more.

The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer are described in US Pat. No. 4,500,626, No. 57.
The relationships described in the column can also be applied to the present application. The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In the constituent layers of the dye-fixing element and the light-sensitive material, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive material and the dye-fixing element. Specific examples include (2) of JP-A-62-253159.
5), pages 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 P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X).
-22-3710) are effective. In addition, JP
Silicone oils described in JP-A-2155953 and JP-A-63-46449 are also effective.

The constituent layers of the dye-fixing element and the light-sensitive material 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 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

Various surfactants can be used in the constituent layers of the dye-fixing element and the light-sensitive material for the purpose of improving coating properties, improving releasability, preventing static charge, and accelerating development. Specific examples of the surfactant are described in JP-A-62-173463 and JP-A-62-1834.
No. 57, etc.

An anti-fading agent may be used in the dye-fixing element or the light-sensitive material. 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 (2
7) to (29), JP-A-63-199248,
-75568 and 1-74272. Examples of useful anti-fading agents are disclosed in
No. 215272, pages (125) to (137). An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a photosensitive material. . 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 dye fixing element and the light-sensitive material. 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 material. As an example, K.K. Veenkataraman
Hen "The Chemistry of Synthe
tic Dyes ", Volume V, Chapter 8, JP-A-61-143
No. 752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. 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 dye-fixing element or a constituent layer of a light-sensitive material.
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).

A matting agent can be used for the dye fixing element and the light-sensitive material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. In addition, the constituent layers of the dye-fixing element and the light-sensitive material 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-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the dye fixing element and / or the light-sensitive material. 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 generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material 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 add a base and / or a base precursor to the dye-fixing element from the viewpoint of improving the storability of the light-sensitive material. 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 material and the dye-fixing element.

In the present invention, various development terminators can be used in the dye-fixing element and / or the light-sensitive material 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 dye fixing element and the photosensitive material, 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 the binder for the dye fixing element and the constituent layer of the photosensitive material, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. 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 employed, the use of the above superabsorbent polymer makes it possible to rapidly 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, more preferably 10 g or less, and even more preferably 7 g or less per 1 m ² .

The constituent layers (including the back layer) of the dye-fixing element or the light-sensitive material are used for the purpose of improving film properties such as dimensional stabilization, curling prevention, adhesion prevention, cracking of the film and pressure sensitivity. 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. .

The photothermographic material used in the present invention basically has a photosensitive silver halide and a binder on a support, and further comprises an organic metal oxidizing agent if necessary.
A dye-donating compound (which may also serve as a reducing agent as described later) and the like can be contained. 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 photothermographic material, 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. In photothermographic materials,
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 can be provided.

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.

The silver halide emulsion may be used as it is after unripe ripening, but usually it is used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, selenium sensitization method, or the like can be used alone or in combination for an emulsion for a conventional light-sensitive material. 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 a methine dye 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 reducing agent used in the present invention, those known in the field of photothermographic materials 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. U.S. Pat. No. 4,500,626 is an example of a reducing agent used in the present invention.
Nos. 49-50, No. 4,483,914, No. 30
Columns 31, 31 and 4,330,617, 4,590,1
No. 52, No. (17) of JP-A-60-140335
(18), pp. 57-40245, pp. 56-1387
No. 36, No. 59-178458, No. 59-53831
Nos. 59-182449 and 59-182450
No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-19854
No. 0, No. 60-181742, No. 61-259253
Nos. 62-244444, 62-131253 to 62-131256, European Patent No. 220,
746A2, pages 78 to 96, and the like. U.S. Pat. No. 3,039,869
Combinations of various reducing agents, such as those disclosed in US Pat.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, in order to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing 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) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, 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.
The amount is from 01 to 20 mol, particularly preferably from 0.1 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 are described in T.W. H. Jam
es, "The Theory of the Pho
toggressive process "4th edition 291-
Pages 334 and 354 to 361, JP-A-58-123
No. 533, No. 58-149046, No. 58-1490
No. 47, No. 59-111148, No. 59-12439
Nos. 9, 59-174835 and 59-231439
Nos. 59-231540, 60-2950, 60-2951, 60-14242, and 60-2
No. 3474, No. 60-66249, and the like.

As another example of the dye donating compound,
Compounds having a function of releasing or generating a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI]. (Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like latent image. (Dye-Y) _n -Z corresponding to or opposite to the photosensitive silver salt having the formula (I), or Dye is released, and the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusibility with _n- Z, n represents 1 or 2, and when 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) corresponding to the development of silver halide, and is to form a diffusible dye image (negative dye image) corresponding to the development of silver halide.
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,
No. 396, JP-A-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.

More preferred are EP 220,746 A2, JP-A-87-6199, US Pat. No. 4,783,396, and JP-A-63-2016.
No. 53, 63-201654 and the like, compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268
No. 42, a compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group in one molecule.
No. 71344 describes that a PO-X bond (X
Has the same meaning as described above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Compounds having a bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group are exemplified. Also, Japanese Patent Application Laid-Open
Compounds disclosed in JP-A-161237 and JP-A-1-161342, in which a single bond is cleaved after reduction by a π bond conjugated to an electron-accepting group to release a diffusible dye, can also be used. Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Examples are EP 220,746 A2 or US Pat. No. 4,783,3.
No. 96, compounds (1) to (3), (7) to
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53)-(59),
(64), (70) and compounds (11) to (23) described in Published Technical Report 87-6199.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and which releases a diffusible dye upon reaction with an oxidized form of a reducing agent. Specifically, 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). Since this compound does not need to use another reducing agent, it is preferable because there is no 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. Specific examples of the DRR compound include the compounds described in the aforementioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to
(3), (10) to (13), (16) to (19),
(28)-(30), (33)-(35), (38)-
(40), (42) to (64) are preferred. The compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful. Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds obtained by combining an organic silver salt and a dye (Research Disclosure Magazine, May 1978, pages 54 to 58, etc.); Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
35,957, Research Disclosure Magazine, 1
And a leuco dye (US Pat. Nos. 3,985,565 and 4,022,617) can also be used.

Hydrophobic additives such as a dye-donating compound and a diffusion-resistant reducing agent can be introduced into a layer of a light-sensitive material 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. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles 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, those mentioned as surfactants on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat.
No. 0,626, columns 51 to 52.

As a method of exposing and recording an image on a photosensitive material, 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, Using a copier exposure device or the like, a method of scanning and exposing an original image through a slit or the like, a method of exposing image information by emitting a light emitting diode, various lasers and the like via an electric signal, exposing an image information to 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 material,
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),
Inorganic compounds typified by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The light-sensitive material 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 transfer 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 system, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent 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 in a method of imparting them to the dye fixing element, the light-sensitive material, 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 imparting a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
6) There is a method described on page. Further, the solvent can be used by being incorporated in advance in the light-sensitive material or the dye-fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote the dye transfer, a system in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material 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. In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As a heating method in the developing and / or transferring 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 used. 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.

[0054]

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

Example 1 First, an example in which the coating density of the mordant is changed according to the first aspect will be described. Table IA to Table IE, Table
Dye-fixing elements (101) to (115) having the constitutions shown in II-A to Table II-C and Table III-A were prepared.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

[Table 9]

Water-soluble polymer (1) Dextran (molecular weight 70,000)

[0066]

Embedded image

[0067]

Embedded image

Fluorescent brightener (1) 2,5-bis (5-t-benzoxazol (2)) thiophene High-boiling organic solvent (1) Empara 40 (Ajinomoto Co., Inc.)
Matting agent (1) Benzoguanamine resin (average particle size 15 μm)

[0069]

Embedded image

[0070]

Embedded image

Here, the dye fixing elements (101) to (10)
5) is a comparative dye-fixing element in which various mordants are applied to one mordant layer. Further, the dye fixing elements (106) to (11)
0) are dye-fixing elements (101) to (105), respectively.
The dye-fixing element of the present invention has two mordant layers as shown in Table II-B without changing the sum of the mordant type and the thickness of the mordant layer and the total coating amount of the mordant. The dye-fixing elements (111) to (115) are respectively the dye-fixing elements (1).
01) to (105), without changing the sum of the mordant type and the thickness of the mordant layer and the total coating amount of the mordant, the dye-fixing element of the present invention in which the mordant layer is formed into three layers as shown in Table II-C. is there. The dye-fixing elements (101) to (115) all have the same number of mordant sites applied per unit area (the number of portions that give mordant power) and are equal to 14.15 mmol / m.
^The amount of each mordant applied was adjusted to be ² .

A photosensitive element commercially available from Fuji Photo Film Co., Ltd. under the name of Fujis Pictrostat Donor Film PS-DF and the dye fixing elements (101) to
In combination with (115), the image was processed using a Fujis Pictrostat 100 (manufactured by Fuji Photo Film Co., Ltd.) as an image recording apparatus. The development temperature during processing is 80 ° C,
The development time was 15 seconds. As a result, a gray image in which the density changed stepwise was obtained.

The reflection density of the color image transferred to each dye fixing element was measured with an X-Rite 310 densitometer. Also,
Light emitted from the xenon light is applied to each dye fixing element for 3 times.
After three days, the reflection density of the color image remaining on the dye-fixing element was measured. Next, the ratio of the dye remaining after the fading test to the density before the fading test was graphed, and the remaining ratio of the dye at the image density of 1.0 before the fading test was determined. Table III-B shows the thus-obtained dye remaining ratio 3 days after the fading test and the maximum density before the fading test.

[0074]

[Table 10]

From these results, the density of the mordant was changed, and the density of the mordant was higher in the mordant layer closer to the support as compared with the comparative dye-fixing element in which the mordant was uniformly applied to the single mordant layer. It can be seen that the dye-fixing element of the present invention can enhance light fastness without changing the maximum density. Further, a copolymer of a plurality of mordants (eg, a copolymer of mordant (1) and mordant (2)), a mixed system of a plurality of mordants (eg, a mixed system of mordant (1) and mordant (2)) As a result of the same evaluation, the same result as described above was obtained.

Example 2 Next, an example of the dye fixing element according to the second aspect of the present invention, which includes a mordant having a higher mordant power as the mordant layer is closer to the support of the dye fixing element, will be described. About the combination of the mordant (3) and the mordant (5), Table IA to Table IE, Table II-A to Table II
-B, and the dye-fixing element (11
6) to (119) were prepared. The mordant power of these mordants is from the highest concentrations of the dye fixing element (103) and the dye fixing element (105) in Table III-B, which indicates that mordant (3) <mordant (5). The dye fixing element (116) is 2
This is a comparative dye-fixing element in which various mordants are mixed and applied to a single mordant layer. The dye-fixing element (117) is a comparative dye-fixing element in which a mordant having a strong mordant power is applied to the mordant layer away from the support, contrary to the present invention. The dye-fixing elements (118) and (119) are dye-fixing elements of the present invention in which a mordant having a higher mordant power is applied to the mordant layer closer to the support.

The dye fixing elements (116) to (119)
Then, the same processing as in Example 1 was performed to obtain a gray image in which the density changed stepwise.

The image transferred to each dye-fixing element was
After leaving for 1 day in an environment of 70 ° C. and 70% RH, a thin section was cut out, and the section was observed with an optical microscope. In the dye-fixing element (116), the dye is uniformly present in the mordant layer, and in the dye-fixing element (117), the dye concentration is higher in the mordant layer near the surface of the dye-fixing element, and the dye-fixing elements (118) and ( 1
In 19), it was observed that the mordant layer closer to the support of the dye-fixing element had a higher dye concentration. This image was subjected to the same fading test as in Example 1. The results are shown in Table IV.

[0079]

[Table 11]

From Table IV, it can be seen that the mordant layer closer to the support of the dye-fixing element, the dye-fixing element of the present invention containing a mordant having a higher mordant power can increase the maximum density without reducing the light fastness. . Further, a dye-fixing element coated such that the density of the mordant having a strong mordant power is higher in the mordant layer closer to the support [eg, the second layer is formed into three layers as shown in Table II-C, and the mordant (3) is added to each layer. 0.4 g / m ² at a time, also mordant (5) 1.0 g / m ² to a 2-a layer, 0.75 g / m ² to the 2-B layer, 0 g / m ² to a 2-C layer The same evaluation was performed for the dye-fixing element obtained using the same method, and the same result was obtained.

[0081]

According to the present invention, a dye-fixing element in which the mordant layer is divided into a plurality and the mordant density is sequentially reduced from the support side, and a dye-fixing element in which the mordant layer is divided into a plurality and mordants having different mordant powers are combined. It can be seen that a dye-fixing element using a mordant having a higher mordant power as the mordant layer is closer to the support is more excellent in light fastness and sharpness of an image than when the mordant layer is a single layer.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 8/24-8/28 G03C 8/56

Claims (2)

(57) [Claims] 1. A dye-fixing element used in a photographic method for forming an image by diffusion-transferring a dye, wherein the dye-fixing element has at least two or more mordant layers on a support and is close to the support. A dye-fixing element, wherein the mordant layer has a higher mordant density in the mordant layer. 2. A dye-fixing element used in a photographic method for forming an image by diffusion transfer of a dye, wherein the dye-fixing element has at least two or more mordant layers on a support and is close to the support. A dye-fixing element, wherein the mordant layer contains a mordant having a higher mordant power.