JPH06194802A - Dyestuff fixing element - Google Patents

Abstract

PURPOSE:To provide a dyestuff fixing element capaple of forming color picture which shows lesser extents of color migration and surface stickiness by adding a thermosetting resin to a layer contg. a mordant and/or to its upper layer. CONSTITUTION:The thermal transfer dyestuff fixing element comprises at least a mordant, a base and/or a base precursor on its substrate and also comprises a thermosetting resin in the layer contg. the mordant and/or in its upper layer. Examples of the thermosetting resin are modified alkyd resins, polyester resins and acrylic resins, etc. Preferably, these resins are used in such a form as an emulsion or an aqueous solution which is solubilized in water and sometimes in a solvent consisting of mixed organic solvents. The amount of the thermosetting resin to be added is within the range of 0.01 to 2.0g/m<2>, and preferably 0.05 to 1.0g/m<2>.

Description

Detailed Description of the Invention

[0001]

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 heat development. For example,
No. 3,531,286, 3,761, for a method of forming a color image by combining a coupler with an oxidant of a developing agent produced by reduction of silver halide.
270, 4,021,240, Belgian Patent No. 8
02,519, Research Disclosure (hereinafter abbreviated as RD) 13742 and the like. Further, a method of forming a positive dye image by heat development by a silver dye bleaching method using silver halide is disclosed in US Pat.
5,957, RD14433, RD15227 and the like. Furthermore, a method of forming or releasing an imagewise diffusible dye from a dye-donor compound with 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 point organic solvent, a method of transferring to a dye-fixing element with a hydrophilic thermal solvent incorporated in the dye-fixing element, a movable dye is heat diffusible or sublimable, and a support And the like have been proposed.

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

[0004]

In the above-mentioned image forming method, the dye-donor element (also referred to as "light-sensitive element") and the dye-fixing element are heat-developed and transferred to form an image, and then the dye-fixing element is raised. When it is stored under humidity in a state where it is overlapped with other dye-fixing elements, the dye moves and the image density decreases, or the dye-fixing element part on a white background becomes so-called "color transfer".
There was a problem. As a method for improving color transfer, Japanese Patent Application Laid-Open No. HEI-3
The method described in −242646 has been proposed, but was insufficient. In addition, there is a problem that the surface has a sticky feeling after the treatment.

[Object of the Invention] An object of the present invention is to provide a dye-fixing element capable of forming a color image with less color transfer and less sticky feeling on the surface.

[0006]

An object of the present invention is to provide a thermosetting resin in a layer containing a mordant and / or an upper layer thereof in a thermal transfer dye fixing element having at least a mordant and a base and / or a base precursor on a support. It was solved by containing.

The thermosetting resin of the present invention exhibits fluidity or softening by heating to show plasticity, and at the same time, a three-dimensional cross-linking bond is generated between molecules due to a chemical reaction, which is cured to become insoluble and infusible, and is heated again. It is a general term for polymer compounds having irreversible properties that never return to the original state, and includes, for example, modified alkyd resins, polyester resins, acrylic resins and the like.
These resins can be used in various shapes,
Preferably, it can be used in the form of an emulsion or water, or an aqueous solution solubilized in a solvent mixed with an organic solvent in some cases. The addition amount of the thermosetting resin is 0.01 to
Can be used in the range of 2.0 g / m ^2, preferably from 0.05 to 1.0 g / m ^2.

As the mordant used in the dye fixing layer, those known in the photographic field can be used. Specific examples thereof 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.
The mordants described in No. 44043 and No. 62-244036 can be mentioned.

Although the photographic element of the present invention can have various embodiments using thermal transfer, a detailed description will be given here of a light-sensitive 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.

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

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

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 .mu.m, more preferably 0.2 to 1.5 .mu.m. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or any other shape. Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1)
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. Conventionally known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods, selenium sensitizing methods and the like can be used alone or in combination for the emulsion of the light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

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

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

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye-fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, a protein such as gelatin derivative, or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, acrylamide weight, and other synthetic polymer compounds. In addition, JP-A-62-1
Super absorbent polymer described in No. 245260, that is,
-COOM or -SO ₃ M (M is hydrogen atom or alkali metal)
Homopolymers of vinyl monomers having the above or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is used, it is possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring 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 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, those known in the field of photosensitive elements can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include US Pat. No. 4,500,626, columns 49 to 50, and US Pat. No. 4,483,914, columns 30 to 30.
Column 1, No. 4,330,617, No. 4,590,152
JP-A-60-140335, pages (17) to (18), ibid. 57-40245, ibid. 56-138736, ibid. 59.
-178458, 59-53831, 59-1
82449, 59-182450, 60-11.
9555 to 60-128436 to 60-12
No. 8439, No. 60-198540, No. 60-1
81742, 61-259253, 62-24.
4044, 62-131253 to 62-13
Up to 1256, there are reducing agents and reducing agent precursors described in EP No. 220,746A2, pages 78 to 96, and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and preferably hydroquinone, Examples thereof include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later. In the present invention, the reducing agent is added in an amount of 0.
001 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, silver can be used as the image forming substance. Further, when the silver ion is reduced to silver under a high temperature condition, a compound that generates or releases a mobile dye in response to this reaction or vice versa, that is, a dye-donating compound may be contained. it can. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
Specific examples of color developers and couplers by TH James
"The Theory of the Photographic Process" Fourth Edition 2
91-334 and 354-361, JP-A-58-
123533, 58-149046, 58-1.
No. 49047, No. 59-111148, No. 59-12.
No. 4399, No. 59-174835, No. 59-231.
No. 539, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

As another example of the dye-donating compound,
A compound having a function of diffusing that does not release the diffusible dye imagewise 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 a linking group, and Z corresponds to or inversely corresponds to a photosensitive silver salt having an imagewise latent image, and causes a difference in diffusivity of the compound represented by (Dye-Y) _n -Z. 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
e-Y may be the same or different. General formula [LI]
Specific examples of the dye-donating compound represented by are the following compounds (1) to (4). In addition, the following ~
Is to form a diffusible dye image (positive dye image) corresponding to the development of silver halide, and is a diffusible dye image (negative dye image) to correspond to the development of silver halide.
Is formed.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972 are described. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho No. 87-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used. An example is U.S. Pat. No. 4,139,389.
No. 4,139,379, JP-A-59-18533.
3 and 57-84453, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat. No. 4,232,107, JP-A-59- 101649, 61-88257, RD
24025 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-5-58
6-142530, U.S. Pat. No. 4,343,893.
No. 4,619,884 and the like, a compound which cleaves a single bond to release a diffusible dye after reduction,
Nitro compounds described in U.S. Pat. No. 4,450,223 that release diffusible dyes after electron acceptance, and nitro compounds described in U.S. Pat. No. 4,609,610 that release diffusible dyes after electron acceptance And the like.

Further, as more preferable ones, European Patent No. 220,746A2, Published Technical Report 87-6199,
U.S. Pat. No. 4,783,396, JP-A-63-201
Nos. 653 and 63-201654, compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ -X (X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A-63-27
No. 1344, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-
No. 271341 and compounds having a CX ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule. In addition, JP-A-1-161
Compounds which do not release diffusible dyes because the single bond is cleaved after reduction by the π bond conjugated with the electron-accepting group described in Nos. 237 and 1-161342 can be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is EP 220,74.
Compounds (1) to (3), (7) to (10), (12), (13), (1 described in 6A2 or U.S. Pat. No. 4,783,396.
5), (23) to (26), (31), (32), (35), (36), (40), (4
1), (44), (53) to (59), (64), (70), Technical Report 87-6
Compounds (11) to (23) described in No. 199.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specific examples include British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, and U.S. Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like. Reducible to silver halide or organic silver salt,
A compound that releases a diffusible dye when the other party is reduced (DR
R compound). This compound does not need to use any other reducing agent, but is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381.
9, 51-104343, RD17465, U.S. Pat. Nos. 3,725,062 and 3,728,113.
No. 3,443,939, JP-A-58-11653.
7, 57-179840, U.S. Pat. No. 4,50.
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, and among them, the compounds (1) to (3),
(10) to (13), (16) to (19), (28) to (30), (33) to (35), (3
8) to (40) and (42) to (64) are preferable. Also, US Patent No. 4,
The compounds described in 639, 408, columns 37 to 39 are also useful. In addition, as a dye-donor compound other than the coupler and the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure 1978
May issue, pages 54 to 58, etc.), azo dyes used in the heat developable silver dye bleaching method (US Pat. No. 4,235,957,
Research Disclosure, April 1976,
Pages 30 to 32), leuco dyes (US Pat. No. 3,983,98)
No. 5,565, No. 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and anti-diffusion reducing agents can be incorporated into the layers of the light-sensitive element by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donor compound used.
It is the following. Also, 1 cc or less for 1 g of binder,
Furthermore, 0.5 cc or less, particularly 0.3 cc or less is suitable.
The dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid,
Various surfactants can be used. For example, those listed 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 stabilizing an image at the same time can be used in the light-sensitive element. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In the constituent layers of the light-sensitive element and the dye-fixing element, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the peelability of the light-sensitive element and the dye-fixing element. A specific example is (25) of JP-A-62-253159.
Page, No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in “Modified Silicone Oil” technical data p.6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-2.
2-3710) is effective. In addition, JP-A-62-2
The silicone oils described in Nos. 15953 and 63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive element and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, 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 compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, 4,254,195, columns 3 to 8, and JP-A-62-174741. 61-88256 (27)
To (29), 63-199248, JP-A-1-755.
68, No. 1-74272 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(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,
The dye fixing element may be supplied from the outside such as a photosensitive element. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent brightening agent in the dye fixing element or supply it from the outside such as a light sensitive element. An example of this is K. Veenkataraman's edition, The Chemistry of Synthetic.
Dyes ”, Vol. V, Chapter 8, compounds described in JP-A-61-143752 and the like can be mentioned. More specific examples include stilbene compounds, coumarin compounds,
Examples thereof include biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The hardener used in the constituent layers of the light-sensitive element and the dye-fixing element is described in US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type 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, improvement of releasability, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
Nos. 944 and 62-135826, or the like, or a hydrophobic surfactant such as an oily fluorine compound such as a fluorine oil or a solid fluorine compound resin such as a tetrafluoroethylene resin described in Can be mentioned.

A matting agent can be used in the light-sensitive element and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Laid-Open Nos. 63-274944 and 6-96, such as S resin beads.
There are compounds described in 3-274952. In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-88256.
No. (26)-(32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a photosensitive element layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and dye transfer 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 in order to enhance the storage stability of the light-sensitive element. In addition to the above, European Patent Publication 210,660 and US Pat. No. 4,740,445.
Combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound) described in JP-A-61-
Compounds that generate a base by electrolysis as described in No. 232451 can also be used as the base precursor.
The former method is particularly 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 terminators can be used in the light-sensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages 31-32.

In the present invention, a support that can withstand the processing temperature is used as a support for the light-sensitive element and the dye-fixing element. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, 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 and other antistatic agents may be coated on the surface of these supports.

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

As a light source for recording an image on the photosensitive element,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM) , JP-A-6
The compounds described in 1-53462 and 62-210432 are preferably used. As the 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. Also, the image information is
Image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Japanese television signal standard (NTSC), image signals obtained by dividing an original image into a large number of pixels such as a scanner, represented by CG and CAD. An image signal created using a computer can be used.

The light-sensitive 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 dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like 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., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower. Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can 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 of applying them to the dye fixing element, the photosensitive element or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method of applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (26).
There is a method described on the page. Alternatively, the solvent may be contained in a microcapsule in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

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

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. And passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0047]

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

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

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Chemical 1]

[0052]

[Chemical 2]

[0053]

[Chemical 3]

[0054]

[Chemical 4]

The fluorescent whitening agent (1) and anti-staining agent (1) of the second layer in Table B were used as an emulsion using a surfactant (1), a high boiling organic solvent (1) and ethyl acetate. The production of this added emulsion will be described. This emulsion was produced by the following steps. Fluorescent brightener (1) 20 g, stain inhibitor (1) 6
0 g and 10 g of the surfactant (1) were dissolved in 650 g of the high boiling point organic solvent (1) and 400 cc of ethyl acetate by heating at 65 ° C. 2,000 cc of the above mixed solution is 15% gelatin aqueous solution
10,000r using a stirring emulsifier at 45 ° C
The mixture was emulsified with stirring at pm for 15 minutes. Further, a dye fixing element (2) was prepared in the same manner as the dye fixing element (1) except that 0.1 g / m ² of an aqueous alkyd resin (Arolone 376J Nippon Shokubai) was added to the fourth layer of Table-B. . Further, a dye fixing element (3) was prepared in the same manner as the dye fixing element (1), except that 0.1 g / m ² of an aqueous acrylic resin (Allolone 76, manufactured by Nippon Shokubai) was added to the fourth layer of Table-B. did.

Further, a light-sensitive element having the constitution shown in Table-C was prepared and designated as light-sensitive element (1).

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Chemical 5]

[0060]

[Chemical 6]

[0061]

[Chemical 7]

[0062]

[Chemical 8]

The above light-sensitive element and dye-fixing element were processed using the image recording apparatus described in Japanese Patent Application No. 63-137104. That is, an original image (a test chart on which yellow, magenta, and cyan wedges having continuously changing densities 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, squeeze with a roller, and then immediately superimpose them so that the dye fixing element and the film surface are in contact with each other,
Using a heat roller adjusted to 80 ℃, 2
Heated for 5 seconds. Then, the light-sensitive element and the dye-fixing element were peeled off, and a clear color image corresponding to the original image was obtained on the dye-fixing element.

Next, the highest density part (Dma
x) and the coating surface of the lowest density portion (Dmin) are overlapped,
After applying a load of 1.5 kg / m ² for 8 hours at 35 ° C. and 85% RH, the density of the lowest density part was measured. The results are shown in Table-D.

[0065]

[Table 5]

As can be seen from Table-D, it is clear that the dye-fixing elements (2) and (3) to which the thermosetting resin is added have improved color transfer. Further, the dye-fixing elements (2) and (3) were less sticky than that of (1).

Claims (1)

[Claims] 1. A thermal transfer dye fixing element having at least a mordant and a base and / or a base precursor on a support, wherein a layer containing the mordant and / or an upper layer thereof contains a thermosetting resin. Fixed element.