JPH06324450A - Dyestuff fixing element - Google Patents

Abstract

PURPOSE:To form images which are nonglossy and are visible with sufficient densities by providing the dyestuff fixing element with a layer contg. a matting agent on the side nearer a base than a dyestuff fixing layer. CONSTITUTION:The system for forming a dyestuff forming element and the dyestuff fixing element on separate bases and forming the images by transferring these elements is provided with the layer contg. the matting agent on the side nearer the base than the dye dyestuff fixing layer. The particles of the matting agent which are not dissipated, deformed and moved in an image forming process are more preferable. In the case of, for example, using of water as a diffusion assistant for the dyestuff and using of a base and high temp. in image formation, the particles are required to be not dissolved in an aq. basic soln. under these conditions. The inorg. matting agent includes natural materials, such as corn starch, and their reformed materials, alkyl acrylates, alkyl methacrylates. The matting agent having 4 to 15mum average grain sizes is more preferable and is required to be provided with some ruggedness in order to make the surface nonglossy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming system for forming an image by providing a dye-forming element and a dye-fixing element on separate supports, superposing both elements and transferring a diffusible dye. It relates to a dye fixing element.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotographic method and diazo photographic method in photographic characteristics such as sensitivity and gradation control. It is used. Among them, many proposals are made to form or release a movable (diffusible) dye imagewise during development, and transfer the movable dye to a dye fixing element having a mordant with a solvent such as water or a thermal solvent. Has been done.

In the method of forming an image by transferring such a movable dye, pressure is often used in order to uniformly perform the diffusion transfer of the dye. However, there is a limit to the pressure applied by the material. Therefore, there is a demand for a material surface shape that allows uniform superposition even under low pressure conditions. Further, the dye fixing material is used for finally utilizing an image in the above image forming system. Therefore, the surface gloss is a performance required for the material. The glossiness required for a material depends on its intended use. A so-called non-glossy surface may be required in order to obtain a texture and to keep the appearance of an image constant under observation conditions.

The non-glossy surface can be usually obtained by providing irregularities on the surface of the material by some means. However, in an image forming system that forms an image by transferring a diffusible dye, it is required that the unevenness of the material surface is not large. Therefore, in order to form a uniform image on the non-glossy surface, it is necessary to strictly control the surface shape. But that was difficult to achieve. Among them, methods using microscopic phase separation of the binder in the layer have been proposed. This method is a good method for providing fine and uniform unevenness, but due to its principle, it was difficult to control the height of the unevenness and the period depending on the manufacturing conditions of the material.

A method using a so-called matting agent, which has been conventionally used, has also been proposed. However, if the matting agent is added to the surface protective layer so as to be used in combination with the surface protecting function to produce a non-glossy surface as is conventionally used, the ratio of the matting agent in the additive layer becomes high, and the image often becomes white. The problem was that the film appeared to be covered.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to form an image by providing a dye-forming element and a dye-fixing element on separate supports, superposing both elements and transferring a diffusible dye. In an image forming system, it is intended to form an image which is non-glossy and visually has a sufficient density.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to form an image by providing a dye-forming element and a dye-fixing element on separate supports, superposing both elements and transferring a diffusible dye. This is solved by a dye fixing element of an image forming system, which has a layer containing a matting agent on the support side of a dye fixing layer.

The present invention will be described in detail below. As the matting agent used in the present invention, various inorganic compound particles,
Organic compound particles, especially polymer particles are used. For the purposes of the present invention, it is preferred that the particles do not disappear, deform or move during the imaging process. For example, when water is used as a dye diffusion aid and basicity and high temperature are used for image formation, it is necessary that it is not dissolved in a basic aqueous solution under the conditions.

Examples of the inorganic matting agent include oxides such as silicon dioxide, titanium oxide and aluminum oxide, alkaline earth metal salts such as barium sulfate, calcium carbonate and magnesium sulfate, and glass particles. Examples of organic matting agents include natural products such as corn starch, cellulose ester, and cellulose ether and modified products thereof, alkyl acrylates, alkyl methacrylates, acrylamides, vinyl esters, olefins, synthetic resins such as styrenes, and the like. Can be mentioned. In addition, JP-A-61
There are compounds described in JP-A-88256 and JP-A-63-274944.

In the present invention, the matting agents may be used alone or in combination of two or more kinds. The matting agent used in the present invention preferably has an average particle size of 4 μm to 15 μm. This is because it is necessary to provide unevenness to some extent in order to make it a non-glossy surface. However, the average particle size is 4 μm
When the following matting agent is further used in combination with the above,
It is preferable because finer and more complicated unevenness can be formed on the surface of the dye fixing element. The amount of matting agent applied is 0.
1 to 3 g / m ² is preferable, and 0.4 to 1.5 g / m ² is particularly preferable.

For the same reason, for example, an average particle size of 12
It is also effective to use two or more kinds of matting agents having different average particle sizes of 4 μm or more, such as using a matting agent of μm and a matting agent having an average particle size of 6 μm. Further, it is also meaningful to further use a matting agent having an average particle size of 4 μm or less. The types of matting agents used in combination may be the same or different.

A hydrophilic binder is preferably used as the binder for the layer containing the matting agent. A specific example will be described later. The thickness of the layer containing the matting agent is important for providing a non-glossy surface, and is preferably 1/10 to 1/2 of the average particle diameter of the matting agent used. The layer containing the matting agent contains a surfactant,
You may add additives, such as a hardener.

As a means for producing a non-glossy surface, in addition to providing a layer containing a matting agent on the support side of the dye-fixing layer in the dye-fixing element, a matting agent is added to the surface protective layer as a surface protecting function. It doesn't matter. However, in that case, the addition amount is preferably 0.10 g / m ² or less.
The matting agent used for the surface protective layer may be the same as or different from the matting agent used for the purpose of the present invention.

The dye-fixing element of the present invention, in a photographic material using a photosensitive silver halide, forms or releases a diffusible dye as a result of development of silver halide, and transfers this diffusible dye to an image receiving material. And used as an image receiving material of a system for obtaining an image. This image forming method is roughly classified into a so-called wet color diffusion transfer method in which development is performed using a processing liquid near room temperature and a heat development diffusion transfer method in which development is performed by heat development. Can also be used as a suitable image receiving material. Since the dye-fixing element of the present invention is particularly preferably used in the heat development diffusion transfer system, it will be described in detail below, but this description will be given except for a portion unique to heat development such as an organic silver salt and a development system. It can be applied in common with the wet type color diffusion transfer system.

The photothermographic material used in the present invention basically has a photosensitive silver halide and a binder on a support and, if necessary, an organometallic hydrochloric acid agent,
A dye-donating compound (which may also serve as a reducing agent as described later) can be contained. 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 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 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. For the photothermographic material,
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 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 having different phases inside the grain and on the grain surface. 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 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type 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 phenylpropiolate, and JP-A-6-36
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 material and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it 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 layers (including the back layer) of the light-sensitive material or the dye-fixing element are for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. 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 photothermographic materials can be used. Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, and U.S. Pat. No. 4,483,914, columns 30 to 31.
Column, ibid. 4,330,617, ibid. 4,590,152
Nos. (17) to (1) of JP-A-60-140335.
8), pages 57-40245, 56-138736.
No. 59-178458, No. 59-53831,
59-182449, 59-182450, 60-119555, 60-128436 to 60-128439, 60-198540,
No. 60-181742, No. 61-259253, No. 62-244404, No. 62-131253 to No. 62-131256, European Patent No. 220,746.
There are reducing agents and reducing agent precursors described on pages 78 to 96 of A2. 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 light-sensitive material 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.
The amount is 01 to 20 mol, particularly preferably 0.1 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.
For specific examples of color developers and couplers, see TH James, "The Theory of the Photographic Process," 4th Edition.
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,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. 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 represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) n-Z represents a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two 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, EP 220,746A2, US Pat. No. 4,783.
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development 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 US Pat. No. 4,232,107, JP-A-59-84453.
No. 101649, No. 61-88257, RD240
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
No. 142530, U.S. Pat. Nos. 4,343,893, 4,619,884, and the like, compounds which release a diffusible dye by cleavage of a single bond after reduction, U.S. Pat. Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents 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 (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,783,3.
Compounds (1) to (3), (7) to (10), (1
2), (13), (15), (23) to (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (59), (64), (70), compounds (11) to (23) described in the open technical report 87-6199, etc. Is.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, 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). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-56-
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. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3),
(10) to (13), (16) to (19), (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 antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling 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 unnecessary for water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing a hydrophobic compound in a hydrophilic colloid,
Various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,62.
No. 6, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding 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, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat.
00,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages (32) to (41), mordants described in JP-A-6-61
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), 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 material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material 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, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256, pages (27) to (29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). The anti-fading agent for preventing the 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 light-sensitive material. . 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 material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. For example, see “The Chemistry of S” edited by K. Veenkataraman.
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-1437
The compounds described in No. 52 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds,
Examples thereof include carbostyryl compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used for the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 4 can be used.
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 material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material. As the matting agent, the same ones as those used in the dye fixing element of the present invention can be used. In addition, the constituent layers of the light-sensitive material 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.
Nos. (26) to (32).

In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. 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 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 in order to enhance the storability of the light-sensitive material. 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 material and the dye fixing element.

In the present invention, various development stoppers can be used in the light-sensitive material 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) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. 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, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses 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 of exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with 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 of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
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 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 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. The above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal created by using a computer represented by Signal, CG and CAD can be used.

The 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 a 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 effective. 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, the temperature 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 light-sensitive material 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 for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

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 material or the dye fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive 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 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 organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

The heating method in the developing and / or transferring step is as follows: contact with a heated block or plate, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared or far infrared lamp heater, etc. 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.

[0053]

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

Example 1

A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. 10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Was used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0057]

[Chemical 1]

[0058]

[Chemical 2]

Next, a method for preparing a dye trapping agent dispersion will be described. Polymer latex (1) (13% solid content)
108 ml, nonionic surfactant (1) 20 g, water 123
While stirring 2 ml of the mixed solution, 600 ml of a 5% aqueous solution of anionic surfactant (1) was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next 1500 ml
Water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0060]

[Chemical 3]

[0061]

[Chemical 4]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. Cyan, magenta, yellow, and electron donor gelatin dispersions were prepared according to the formulations in Table 1, respectively. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, and this solution and an aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed, followed by a homogenizer for 13 minutes,
Dispersed at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0063]

[Table 1]

[0064]

[Chemical 5]

[0065]

[Chemical 6]

[0066]

[Chemical 7]

[0067]

[Chemical 8]

[0068]

[Chemical 9]

[0069]

[Chemical 10]

[0070]

[Chemical 11]

[0071]

[Chemical 12]

[0072]

[Chemical 13]

[0073]

[Chemical 14]

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

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 480 ml of water).
g and 30 mg of silver halide solvent (1) were added, and the temperature was 45 ° C.
The solution (I) and the solution (II) shown in Table 2 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 20 minutes. After 5 minutes, (III) in Table 2
Solution and (IV) solution were added simultaneously at the same flow rate for 25 minutes. Also (I
II), 10 minutes after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a pigment (containing 105 g of water, 1 g of gelatin, 70 mg of pigment (1), 139 mg of pigment (2), and 5 mg of pigment (3) at 45 ° C Which was kept warm) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and 4.1 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Add 1,250 mg of -1,3,3a, 7-tetrazaindene and 1.8 mg of chloroauric acid, and add 60 ° C.
Optimally chemically sensitized with, then antifoggant (3) 200
After adding mg, the mixture was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm
Got

[0077]

[Chemical 15]

[0078]

[Table 2]

[0079]

[Chemical 16]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 783 ml of water).
and 30 mg of silver halide solvent (1) were added, and the mixture was heated to 65 ° C.
The solution (I) and the solution (II) shown in Table 3 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 30 minutes. After 5 minutes, (III) in Table 3
Solution and (IV) solution were added simultaneously at an equal flow rate for 15 minutes. Also (I
II), 2 minutes after the start of the addition of solution (IV), an aqueous solution of a gelatin dispersion of dye (containing 0.9 g of gelatin, 76 mg of dye (1), 150 mg of dye (2), and 5 mg of dye (3) in 95 ml of water) (Incubated at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 2.8 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Add 175 mg of -1,3,3a, 7-tetrazaindene and 1.2 mg of chloroauric acid, and add 60 ° C.
Chemistry optimally with, then antifoggant (2) 163mg
And then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0082]

[Chemical 17]

[0083]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide and 4 parts of sodium chloride).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 48 ° C.
The solution (I) and the solution (II) shown in Table 4 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 8 minutes. 10 minutes later (III) in Table 4
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 100 ml of water and 250 mg of the dye (4) and kept at 45 ° C.) was added all at once. .

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, sodium thiosulfate 9.4 mg and 4-hydroxy-6-methyl. Add 263 mg of -1,3,3a, 7-tetrazaindene and optimally perform chemical sensitization at 68 ° C,
After adding 163 mg of the antifoggant (2), the mixture was cooled.
Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0086]

[Table 4]

[0087]

[Chemical 18]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and 15 mg of silver halide solvent (1) are added, and the temperature is 55 ° C.
The solution (I) and the solution (II) shown in Table 5 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 20 minutes. After 10 minutes, (II in Table 5
Solution (I) and solution (IV) were added simultaneously at an equal flow rate for 20 minutes. In addition, 1 minute after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (a mixture of 1.8 g of gelatin and 180 mg of the dye (4) in 95 ml of water and kept at 45 ° C.) was collectively added. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and 1.0 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. -1,3,3a, 7-Tetrazaindene (46 mg) and chloroauric acid (0.6 mg) were added for optimum chemical sensitization at 68 ° C, and then antifoggant (2) 163 m.
After adding g, it was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm
Got

[0090]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 51 ° C.
The solution (I) and the solution (II) shown in Table 6 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 8 minutes. After 10 minutes, (III) in Table 6
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
One minute after the addition of the solutions (II) and (IV) is completed, an aqueous solution of the dye (water 95
The dye (5) (220 mg) and the dye (6) (110 mg), which had been kept at 45 ° C., in 5 ml of methanol and 5 ml of methanol) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate 4.8 mg and 4-hydroxy-6-methyl were added. Add 1,3,3a, 7-tetrazaindene (250mg) and optimally chemically sensitize at 68 ° C.
Next, 163 mg of antifoggant (2) and 94 mg of potassium iodide were added, and the mixture was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm
35 g were obtained.

[0093]

[Table 6]

[0094]

[Chemical 19]

Photosensitive Silver Halide Emulsion (6) [For blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.3 g, sodium chloride 9 in 695 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 63 ° C.
The solution (I) and the solution (II) shown in Table 7 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 10 minutes. After 10 minutes, (II in Table 7
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 30 minutes. One minute after the addition of the solutions (III) and (IV), an aqueous solution of the dye (66 mg of water and 4 ml of methanol, containing 155 mg of the dye (5) and 78 mg of the dye (6) and kept at 60 ° C.) was put together. Added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and 1.6 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Addition of 95 mg of -1,3,3a, 7-tetrazaindene and 0.31 mg of chloroauric acid at 68 ° C
Optimally chemically sensitized with, then antifoggant (2) 163
After adding mg and potassium iodide 94 mg, it cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0097]

[Table 7]

A light-sensitive material D shown in Table 8 using the above materials
Made 101.

[0099]

[Table 8]

[0100]

[Table 9]

[0101]

[Table 10]

[0102]

[Chemical 20]

[0103]

[Chemical 21]

[0104]

[Chemical formula 22]

Next, how to make the image receiving material will be described. A method for preparing a dispersion of the optical brightener and the stain inhibitor will be described. 25 g of optical brightener (1), 32 g of anti-staining agent (1), 10 g of anionic surfactant (1) and 10 g of anionic surfactant (5) were added to high boiling organic solvent 6
It was dissolved in 90 g and 250 ml of ethyl acetate, added to 1200 ml of 25% gelatin aqueous solution, and dispersed with a homogenizer for 20 minutes at 1250 rpm. To this, 300 ml of water was further added and stirred to obtain a uniform dispersion.

Next, a method for preparing a latex dispersion will be described. 20 g of gelatin and water-soluble polymer (4) 3
After dissolving 0 g in 200 ml of water at 50 ° C., the temperature is lowered to 40 ° C., and 117 g of latex dispersion (1) is added and stirred. The solution was filtered through a 30μ filter in a dissolved state to obtain a uniform dispersion. An image receiving material R101 having the structure shown in Table 9 was produced. Similarly, an image receiving paper material R201 in which the components having the constitution shown in Table 10 were provided on the support shown in Table 11 was produced.

[0107]

[Table 11]

[0108]

[Table 12]

[0109]

[Chemical formula 23]

[0110]

[Chemical formula 24]

[0111]

[Chemical 25]

[0112]

[Chemical formula 26]

[0113]

[Chemical 27]

[0114]

[Chemical 28]

[0115]

[Chemical 29]

[0116]

[Chemical 30]

[0117]

[Chemical 31]

[0118]

[Table 13]

[0119]

[Table 14]

Further, image receiving materials R102 to R120 were prepared in the same manner as in R101 except that the matting agent shown in Table A was added in the addition amount shown in the addition layer shown. However, R110 is the same as R101 of 200 /
490, R117-119 is the first layer of gelatin R1
01 of 900/490. In the same way,
In addition to the matting agent (2) of the fourth layer shown in Table 10, the matting agents shown in Table B were added in the amounts shown in the addition layers shown in the same manner as in the case of R201.
220 was produced. However, in R217 to 219, the gelatin of the first layer is 900/190 of R201.

The type of matting agent is indicated by the material of the particles and the average particle size. The addition layers are shown in Table 9 and Hail 10 as layer names, and the addition amount is shown in g of solid content addition per 1 square meter. The ratio of the average particle diameter of the matting agent and the thickness of the first layer for the case where the matting agent was added to the first layer is shown in the table as "thickness / particle diameter". The thickness of the first layer other than the matting agent is approximately 0.50 μ in R101 to 109, 111 to 116 and 120, approximately 0.21 μ in R110, and 0.9 in R117 to 119.
1μ, 0.20 in R201 to 216, 220
In μ, 217 to 219, it is 0.91 μ.

The above light-sensitive material and image-receiving material were processed using the image recording apparatus described in JP-A-2-84634. That is, a full-color original image is scanned and exposed through a slit, and the exposed light-sensitive material is exposed to water kept at 40 ° C. for 2.5 hours.
After soaking for a second, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface temperature is 80 ° C., the photosensitive material is peeled off from the image receiving material by heating for 17 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

The glossiness of this image was measured with a digital variable angle glossmeter UGV-5D manufactured by Suga Test Instruments Co., Ltd. The results (20 degree gloss) are summarized in Tables A to C. When the glossiness is less than 15, the surface becomes a non-glossy surface, and when the glossiness is 6 or less, a so-called deep matte (matte surface) is formed. Next, using a reflection densitometer, the density of the black portion was measured and shown as the transfer density. In addition, the texture that looks like the image was covered with white was evaluated visually and shown as “texture”. “X” indicates that the image looks like a white coating, and “◯” indicates that the image is good. Further, the uniformity of the transferred image was visually evaluated and shown as "transferability". "○" indicates that the image looks uniform, "△" indicates that it does not affect the uniformity, but does not change the evaluation as an image, and "x" indicates that there is a problem in image uniformity. Is shown.

[0124]

[Table 15]

[0125]

[Table 16]

As can be seen from Table A, the dye-fixing material using the compound of the present invention has a lower glossiness as a matte surface than the comparative examples (101 to 107), a texture which does not make the surface white, and the uniformity of the transferred image. It turns out that you are satisfied. In detail, Comparative Examples 101 to 107 are examples in which a matting agent is added to the surface protective layer, and it is understood that the glossiness decreases and a good matt surface can be obtained as the amount of the matting agent added increases. Further, when a matting agent having a large particle size is used, it is possible to find that the matting property is excellent with a smaller addition amount. However, at the same time, it can be seen that the transferability deteriorates and the image becomes non-uniform as the amount of the matting agent added increases. In addition, in the examples (R104 to 107) in which the matting agent was added to the surface protective layer, it was found that the texture was deteriorated. On the other hand, when a matting agent is added to the support side (first layer) of the mordant layer of the present invention (R108 to 120), it is found that a good matt surface can be obtained without deteriorating both texture and transferability. .
Among them, those having a particle size of less than 4 μ (R108, 10
It can be seen that in 9), the glossiness is slightly high and the matteness is deteriorated. On the contrary, the particle size exceeds 15μ (R119, 12
It can be seen that in 0), the transferability is slightly deteriorated. Further, in the case where the thickness / particle diameter is smaller than 1/10 (R110), it is found that the transferability is slightly deteriorated. Conversely, the thickness / particle size is 1
It can be seen that the glossiness increases a little when the value is larger than / 2 (R117, 118).

From Table B, as in Table A, the dye fixing materials (R208 to 220) using the compound of the present invention are the same as Comparative Examples (R).
201 to 207), lower gloss as a matte surface,
It can be seen that the surface does not turn white, and the uniformity of the transferred image is satisfied. Also, R104 of Table A and Table B
Comparing R204 in Table A with R106 in Table A and R206 in Table B, it can be seen that R204 and 206 are slightly superior in uniformity of transfer. Although this is not shown in the evaluation tables (Tables A and B), the same applies to other image receiving paper materials, and when comparing comparable materials, it is always R2.
Transferability is better for products in the 00s. This effect is
Although not clear, it seems to be the result of not using the water-soluble polymers (2) and (3) in combination with the guanidine picolinate used in the fourth layer of the R200 series image receiving paper material.

Example 2 Image-receiving materials R301 to R320 were prepared in the same manner as R201 to 220 of Example 1 except that the matting agent shown in Table B was added to the first layer or the fourth layer shown in Table 11. Then, the same treatment and evaluation as in Example 1 were performed. As a result, almost the same result as in Example 1 was obtained.

[0129]

[Table 17]

Example 3 A method for preparing the emulsion (7) will be described. (Emulsion for Fifth Layer) Solution I and solution II having the compositions shown in Table 14 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 13 which was well stirred, and then the emulsion having the composition shown in Table 14 was added. Liquid III and IV 3
Added over 5 minutes.

[0131]

[Table 18]

[0132]

[Table 19]

From 18 minutes after the start of addition of the liquid III,
75cc of 0.5% methanol solution of dye (7) over a period of time
Was added. Washing with water, desalting (pH = using sedimentation agent (1)
4.1) and then add 22 g gelatine to pH
= 6.0, pAg = 7.9, and then chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 15. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic emulsion having a grain size variation coefficient of 10.2%, and the average grain size was 0.31 micrometer.

[0134]

[Table 20]

[0135]

[Chemical 32]

[0136]

[Chemical 33]

The method for preparing the emulsion (8) will be described. (Emulsion for Third Layer) Solution I and solution II having the composition shown in Table 17 were simultaneously added over 10 minutes to an aqueous solution having the composition shown in Table 16 which was well stirred, and then the emulsion having the composition shown in Table 17 was added. Liquid III and IV 4
Added over 5 minutes.

[0138]

[Table 21]

[0139]

[Table 22]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent (1) at pH = 3.9), 12 g of gelatin was added to pH = 5.9 and pAg = 7.8. Then, it was chemically sensitized at 70 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of dye (8) (gelatin 5%, sensitizing dye 0.5%) was added. The compounds used for the chemical sensitization are shown in Table 18. The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a grain size variation coefficient of 12.6%, and the average grain size was 0.32 micrometer.

[0141]

[Table 23]

[0142]

[Chemical 34]

A method for preparing the emulsion (9) will be described. (Emulsion for First Layer) Solution I and solution II having the composition shown in Table 20 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 19 which was well stirred, and then the composition shown in Table 20 was added. Solution III and IV solution 2
Added over 5 minutes.

[0144]

[Table 24]

[0145]

[Table 25]

Further, after washing with water and desalting (performed with a compound represented by the precipitating agent (1) at pH = 3.8), 20 g of gelatin was added to pH = 6.6 and pAg = 8.0. Then, it was chemically sensitized at 58 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of dye (9) (gelatin 5%, sensitizing dye 1%) was added. The compounds used for the chemical sensitization are shown in Table 21. The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.22 micrometer.

[0147]

[Table 26]

[0148]

[Chemical 35]

Next, a method for preparing a gelatin dispersion of the dye-donor compound will be described. Magenta dye donating compound (2) 14.64 g, reducing agent (1) 0.8 g, antifoggant (4) 0.20 g, anionic surfactant (2) 0.
4 g and 5.1 g of high boiling point solvent (2) were weighed, and ethyl acetate 7
0 ml was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution, 71 g of a 14% lime-processed gelatin solution, and 220 cc of water were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a magenta dye-donor compound.

[0150]

[Chemical 36]

7.3 g of the cyan dye-donating compound (3),
Cyan dye donating compound (4) 10.6 g, reducing agent (1) 1.0 g, antifoggant (4) 0.30 g, anionic surfactant (2) 0.4 g, high boiling point solvent (2) 9.
8 g was weighed, 40 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. After stirring and mixing this solution with 71 g of a 14% solution of lime-processed gelatin and 260 cc of water,
Disperse with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a cyan dye-donor compound.

[0152]

[Chemical 37]

Yellow dye-donor compound (2) 18.8
g, reducing agent (1) 1.0 g, antifoggant (4) 0.1
3 g, anionic surfactant (2) 1.5 g, dye (1)
2.1 g and 7.5 g of the high boiling point solvent (2) were weighed, 45 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 71% of this solution and 14% of lime-processed gelatin
g and 160 cc of water by stirring and mixing, and then 1 with a homogenizer
Dispersed for 0 minutes at 10,000 rpm. This dispersion is referred to as a yellow dye-donor compound dispersion.

[0154]

[Chemical 38]

From these, the light-sensitive material D as shown in Table 22
201 was configured.

[0156]

[Table 27]

[0157]

[Table 28]

[0158]

[Chemical Formula 39]

[0159]

[Chemical 40]

[0160]

[Chemical 41]

[0161]

[Chemical 42]

[0162]

[Chemical 43]

The high boiling point solvent (5) is triisononyl phosphate. A method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide having an average particle size of 0.15 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate are added to 100 ml of a 4% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm are milled. Was crushed for 30 minutes. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, evaluation was performed by the following exposure and processing. Using the above light-sensitive material and the image-receiving materials R201 to 220 produced in Example 1, Japanese Patent Application No. 63-281418
No. 63-204805, and a laser exposure apparatus described in No. 63-204805 was used to perform exposure under the conditions shown in Table 23. The dampening water is supplied to the exposed photosensitive material D201 emulsion surface with a wire bar,
Then, they were superposed so that the image receiving material was in contact with the film surface. An image receiving material was peeled off from the light-sensitive material by using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was 85 ° C., and the image was obtained on the image receiving material.

[0165]

[Table 29]

A black print of uniform density was produced by adjusting the exposure amount of each laser using the above-mentioned exposure device. This image was evaluated in the same manner as in Example 1. The results are summarized in Table C.

[0167]

[Table 30]

As can be seen from Table C, the dye-fixing material using the compound of the present invention has a lower glossiness as a matte surface than the comparative examples (201 to 207), a texture that does not make the surface white, and the uniformity of the transferred image. It turns out that you are satisfied. As seen in detail, Comparative Examples 201 to 207 are examples in which a matting agent was added to the surface protective layer, and it was found that as the amount of the matting agent added increased, the glossiness decreased and a good matte surface was obtained. Further, when a matting agent having a large particle size is used, it is possible to find that the matting property is excellent with a smaller addition amount. However, at the same time, it can be seen that the transferability deteriorates and the image becomes non-uniform as the amount of the matting agent added increases. In addition, in the examples (204 to 207) in which the matting agent was added to the surface protective layer, it was found that the texture was deteriorated. On the other hand, when a matting agent is added to the support side (first layer) of the mordant layer of the present invention (208 to 220), it is found that a good matt surface can be obtained without deteriorating both texture and transferability. . Among them, those with a particle size of less than 4μ (208, 209) are
It can be seen that the glossiness is slightly high and the matteness is deteriorated. On the contrary, when the particle size exceeds 15 μ (219, 220), the transfer property is found to be slightly deteriorated. Also, the thickness / particle size is 1 /
It can be seen that in the example (210) smaller than 10, the transferability is slightly deteriorated. On the contrary, when the thickness / particle size is larger than 1/2 (217, 218), the glossiness is slightly increased.

[0169]

When the image receiving material (dye fixing material) of the present invention is used, a good matte surface image satisfying all of low glossiness as a matte surface, texture not giving a white surface, and uniformity of transferred image can be obtained. be able to.

Claims (3)

[Claims] 1. A dye-fixing element for an image-forming system for forming an image by providing a dye-forming element and a dye-fixing element on separate supports, superposing the two elements, and transferring a diffusible dye. A dye fixing element comprising a layer containing a matting agent on the support side of the dye fixing layer. 2. The dye fixing element according to claim 1, wherein the matting agent added has an average particle diameter of 4 μm or more and 15 μm or less. 3. The dye fixing element according to claim 1, wherein the layer containing the matting agent has a thickness of 1/1 of the average particle diameter of the matting agent.
A dye fixing element, which is 0 or more and 1/2 or less.