JPH07209836A - Dye fixing element - Google Patents

Abstract

PURPOSE:To obtain a dye fixing element giving a high transfer density in a color diffusion transfer process. CONSTITUTION:A compd. represented by the general formula is used in a dye fixing layer or other constituent layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye fixing element used in a color diffusion transfer method, and more particularly to a dye fixing element capable of forming a transferred dye image having a high density.

[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, color diffusion that forms or releases a diffusible dye imagewise by development and transfers this diffusible dye to a dye fixing element (image receiving material) having a dye fixing layer with a solvent such as water or a thermal solvent. A transfer method is known.

In the color diffusion transfer method, it is important to form a transferred dye image having a high density. for that reason,
In the color diffusion transfer method, some means for promoting the formation or release of the diffusible dye or for promoting the diffusion transfer of the dye. Among these, pH during image formation
Is the most effective, and a compound that gives a diffusible dye image by this means (dye-donor compound)
It is advantageous that the environmental condition in which is present can be distinguished at the time of image formation and at the time of storage before that.

As a means for distinguishing between pH during storage and pH during image formation, European Patent 210,660B (US Pat. No. 4,740,445, JP-A-62-129848).
No. 62-187847), the method for generating an alkali (base) is particularly advantageous. This method
In this method, a base is generated as a result of a reaction between a poorly water-soluble metal compound and a compound capable of releasing a base by forming a complex with a metal of the metal compound (referred to as a complex-forming compound). Usually, the complex-forming compound is contained in the constituent layer of the dye-fixing element, the water-insoluble metal compound is contained in the photosensitive element,
During image formation, both elements are superposed and a complex formation reaction is caused using water as a medium to raise the pH in the light-sensitive element and the dye-fixing element.

[0005]

In this method, it was necessary to use a large amount of the above complex-forming compound in order to obtain the base necessary for image formation. Therefore, there is a demand for an image formation promoting means which is different from this method or can be used in combination with this method. Therefore, an object of the present invention is to provide a dye fixing element for a color diffusion transfer method capable of forming a transfer dye image having a high density, and in another aspect, a small amount of a base is generated during image formation. However, the object is to provide a dye fixing element for color diffusion transfer capable of forming a transfer dye image having a sufficiently high density.

[0006]

The object of the present invention is to provide a support having at least one dye-fixing layer, and the dye-fixing layer or other layers having a compound represented by the following general formula (1). Was achieved by a dye-fixing element used in a color diffusion transfer process characterized by containing General formula (1)

[0007]

[Chemical 2]

The present invention will be described in detail below. In formula (1), the aliphatic hydrocarbon group for R ₀ includes an alkyl group, an alkenyl group, and an alkynyl group, and the aromatic hydrocarbon group includes a monocyclic or bicyclic aryl group, and a heterocyclic group. The group is a 5- or 6-membered ring group having at least one of a nitrogen atom, an oxygen atom and a sulfur atom in the ring, and may be condensed with a benzene ring. Each group of R ₀ may have a substituent, and as the substituent, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group,
A halogen atom and an acyloxy group are preferred. R ₀ preferably does not contain an epoxy group. In the present invention,
Particularly preferred are compounds represented by the following general formula (1a), (1b) or (1c).

[0009]

[Chemical 3]

In the general formulas (1a) and (1b), R ₁
And R ₂ represents a same group as R _0, may have the same substituents as those described in R _0. In particular, R ₁ and R ₂ are preferably an alkyl group having 20 or less carbon atoms (including those having a substituent) or a phenyl group (including those having a substituent). It is preferable that R ₁ and R ₂ do not contain an epoxy group. In the general formula (1b), n represents an integer of 1 to 30, preferably 1 to 20. In the general formula (1c), X is an alkoxycarbonyl group,
It represents an alkyl-substituted aminocarbonyl group, a phenyl group (including those having a substituent, such as a SO ₂ Na group), and Y represents a hydrogen atom or a lower alkyl group. x and y are numerical values showing the molar ratio of each monomer, and x: y
= 1: 5 to 10: 1, and particularly preferably 1: 3 to 6: 1.

Specific examples of the compound represented by the general formula (1) used in the present invention are shown below. However, the present invention is not limited to these.

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6]

The compound of the present invention can be obtained by a general method for synthesizing an epoxy group from an aldehyde, a ketone or a vinyl group.

The compound of the present invention may be water-soluble or oil-soluble. When it is water-soluble, it can be used as it is as an aqueous solution, and when it is oil-soluble, it can be emulsified and used as an emulsion. It can also be used as a solid dispersion. When used as an emulsion,
The smaller the particle size, the more effective. The particle size is 1 μm
To 0.01 μm is preferable, and 0.35 μm is more preferable.
m to 0.05 μm.

The addition amount of the compound of the present invention is preferably 0.01 to 4.0 g / m ² , and more preferably 0.0.
5 to 2.0 g / m ² . The compound of the present invention may be contained in any constituent layer on the side where the dye fixing layer is present.
For example, there are a dye fixing layer, a protective layer, and a layer provided between the dye fixing layer and the support.

The dye-fixing element of the present invention has at least a dye-fixing layer on a support, and the support may be shared with the light-sensitive element (in this case, between the dye-fixing element and the light-sensitive element). It is preferable to provide a white reflective layer), and a support other than the photosensitive element may be used. Regarding the relationship between the dye-fixing element and the light-sensitive element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in US Pat. No. 4,500,626 at column 57 can be applied to the present invention. The dye fixing element preferably used in the present invention contains a mordant in the dye fixing layer. As the mordant, those known in the field of color diffusion transfer method can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-8.
The mordants described in Nos. 8256 to (32) to (41), those described in JP-A Nos. 62-244043 and 62-244036, and the like can be mentioned. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 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 present invention, European Patent 210,66
No. 0B (U.S. Pat. No. 4,740,445, JP-A-62-
It is preferable to use the compound of the general formula (1) of the present invention in combination with the alkali (base) generation method described in No. 129848 and No. 62-187847). That is, the dye fixing element of the present invention is preferably a combination of the compound of the general formula (1) and the complex-forming compound defined in the above patent. Here, as the complex-forming compound, the complex-forming compounds described in JP-A-62-129848, page 4, upper left column, line 5 to page 6, lower right column, bottom to line 8,
And the complexing agents described in JP-A No. 62-187847, from page 12, lower right column, line 2 to page 14, upper right column, bottom line. In the above-mentioned point, a metal compound which is hardly soluble in water and which is suitable for use in combination with a complex-forming compound or a complexing agent is described. In this particular embodiment of the invention, these metal compounds are used in the light-sensitive element. The amount of the complex-forming compound used is appropriately 50% by weight or less, preferably 0.01 to 40% by weight, based on the weight of the coating film on the support. When used in combination with the compound of the general formula (1) of the present invention, a high density transfer dye image can be obtained in a smaller amount than in the case where the compound of the general formula (1) is not used.

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 at around 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 the organic silver salt, the development system and the like which are peculiar to the heat development. It can be applied in common with the wet type color diffusion transfer system.

The heat-developable photosensitive element used in the present invention basically has a photosensitive silver halide and a binder on a support, and further, if necessary, an organometallic salt oxidizing 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 element, but it 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 having photosensitivity in 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 element,
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 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 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 can 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. 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, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides 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 becomes 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 element or the dye-fixing element are 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 photothermographic elements 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 is optionally added 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.
The amount is 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, when silver ions are reduced to silver in the photosensitive element under high temperature conditions, in response to this reaction,
Alternatively, a compound that produces or releases a mobile dye correspondingly, that is, a dye-donor compound is contained. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
Specific examples of color developing agents and couplers can be found in T.W. H. James
4th "The Theory of the Photographic Process"
Pp. 291-334 and 354-361, JP-A-5
8-123533, 58-149046, 58
-149047, 59-1111148, 59-
124399, 59-174835, and 59-2.
No. 31539, No. 59-231540, No. 60-29.
No. 50, No. 60-2951, No. 60-14242,
No. 60-23474, No. 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 linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusibility of the compound represented by (Dye-Y) _n -Z, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility from _n- Z, n represents 1 or 2, and when n is 2, two 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 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 and 4,619,884, 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 ′ is synonymous with 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 which 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-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. 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, the couplers and the general formula [L
I] as a dye-donating compound other than I], a dye-silver compound in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, p. 54-58, etc.), an azo dye used in a heat-developable silver dye bleaching method. (U.S. Pat. No. 4,235,
957, Research Disclosure, 1976.
April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617, etc.) and the like can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layers of the light-sensitive element 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 insoluble in 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 element. Specific compounds preferably used are described in US Pat. No. 4,500,62.
No. 6, 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 releasability of the light-sensitive element 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 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, coumarans 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 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, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive element. As an example, K. Veenkataraman edition `` The Chemistry of
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-143
Examples thereof include the compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive element and the dye-fixing element, 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 slipperiness, 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
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 photosensitive element. 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 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.
Nos. (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element. 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 transfer of a dye are simultaneously carried out 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 the present invention, various development stoppers can be used in the light-sensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to 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 after proper development to lower the concentration of the base in the film to stop the 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 element 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.

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

As a light source for recording an image on the photosensitive element,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. 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 (POM)
The nitropyridine-N-oxide derivative as described above 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 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 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 in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

In order to accelerate 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 brought into contact, 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 heat developing 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.

[0058]

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

Example 1 A method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution,
30 using glass beads with an average particle size of 0.75 mm in a mill
Grind for minutes. 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 nonyl phenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% aqueous gelatin 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.

[0061]

[Chemical 7]

[0062]

[Chemical 8]

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.

[0064]

[Chemical 9]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. The cyan, magenta, and yellow dye-donating compounds and the gelatin dispersion of the electron donor were adjusted according to the formulations shown in Table 1. That is, each oil phase component was heated and dissolved at about 60 ° C to form a uniform solution, and this solution and about 6
The aqueous phase components heated to 0 ° C were added, and the mixture was stirred and mixed, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0066]

[Table 1]

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18]

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 1 g of gelatin, 70 mg of pigment (1), 139 mg of pigment (2), and 5 mg of pigment (3) in 105 ml of water 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. 250 mg of -1,3,3a, 7-tetrazaindene and 1.8 mg of chloroauric acid were added, optimally chemically sensitized at 60 ° C, and then cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.30 μm
g was obtained.

[0079]

[Chemical 19]

[0080]

[Table 2]

[0081]

[Chemical 20]

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 a pigment (containing 0.9 g of gelatin, 76 mg of pigment (1), 150 mg of pigment (2), and 5 mg of pigment (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. -1,3,3a, 7-Tetrazaindene (175 mg) and chloroauric acid (1.2 mg) were optimally chemically sensitized at 60 ° C, and then antifoggant (2) (163 mg) was added, followed by cooling. Thus, the average particle size of 0.
635 g of 50 μm monodisperse cubic silver chlorobromide emulsion was obtained.

[0084]

[Table 3]

[0085]

[Chemical 21]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride in 690 ml of water).
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 and 250 mg of the dye (4) in 100 ml of water 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 the pH to 6.0 and pAg to 7.6, and 9.4 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. 263 mg of -1,3,3a, 7-tetrazaindene was added, optimal chemical sensitization was performed at 68 ° C, and 163 mg of antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0088]

[Table 4]

[0089]

[Chemical formula 22]

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 pH to 6.0 and pAg to 7.6, and 1.0 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. 46 mg of -1,3,3a, 7-tetrazaindene and 0.6 mg of chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then 163 mg of antifoggant (2) was added, followed by cooling. Thus, the average particle size of 0.
635 g of a 45 μm monodisperse cubic silver chlorobromide emulsion was obtained.

[0092]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (20 g gelatin in 690 ml water, 0.5 g potassium bromide, 5 sodium chloride)
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 were kept warm at 45 ° C., were added all at once to 100 ml of methanol and 5 ml of methanol.

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. -1,3,3a, 7-Tetrazaindene (250 mg) was added for optimum chemical sensitization at 68 ° C., followed by antifoggant (2) (163 mg) and potassium iodide (94).
After adding mg, it cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0095]

[Table 6]

[0096]

[Chemical formula 23]

Photosensitive silver halide emulsion (6) [For blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride 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) was completed, an aqueous solution of the dye (66 ml 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. -1,3,3a, 7-Tetrazaindene (95 mg) and chloroauric acid (0.31 mg) were added for optimum chemical sensitization at 68 ° C, and then 163 mg of antifoggant (2) and 94 mg of potassium iodide were added. , Cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0099]

[Table 7]

Photosensitive material 2 shown in Table 8 using the above
I made 01.

[0101]

[Table 8]

[0102]

[Table 9]

[0103]

[Table 10]

[0104]

[Chemical formula 24]

[0105]

[Chemical 25]

[0106]

[Chemical formula 26]

An image receiving material 101 having the structure shown in Table B was prepared. Also, the image receiving material 10 except that the comparative compound shown in Table E and the compound of the present invention were used in the fourth layer of Table B in the amounts shown in Table E
In the same manner as in No. 1, image receiving materials 102 to 115 were prepared.

[0108]

[Table 11]

[0109]

[Chemical 27]

[0110]

[Chemical 28]

[0111]

[Chemical 29]

[0112]

[Chemical 30]

Using the above light-sensitive material and image-receiving material, processing was carried out using the image recording device described in JP-A-2-84634. That is, a full-color original image was scanned and exposed through a slit, the exposed light-sensitive material was immersed in water kept at 40 ° C. for 5 seconds, and then squeezed with a roller to immediately overlay the image-receiving material with the film surface. Next, using a heat drum whose temperature was adjusted so that the temperature of the water-absorbed film surface became 80 ° C,
After heating for 15 seconds and peeling the photosensitive material from the image receiving material,
A clear color image corresponding to the original image was obtained on the image receiving material.

The reflection density was measured using a densitometer (FCD3) manufactured by Fuji Photo Film Co., Ltd. with the highest sensitivity (Dmax). The results are summarized in Table E.

[0115]

[Table 12]

As can be seen from Table E, the image receiving materials (104 to 115) using the present invention are the image receiving materials (1
01) or an image receiving material using a comparative compound (102)
It can be seen that the maximum density (Dmax) is higher than that of

Example 2 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. The silver halide solvent (1) is the same as that used in Example 1.

[0118]

[Table 13]

[0119]

[Table 14]

Further, from 18 minutes after the start of addition of the solution III,
75cc of 0.5% methanol solution of dye (7) over a period of time
Was added. Washing with water, desalting (using the precipitating agent (1), pH =
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 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.

[0121]

[Table 15]

[0122]

[Chemical 31]

[0123]

[Chemical 32]

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.

[0125]

[Table 16]

[0126]

[Table 17]

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.

[0128]

[Table 18]

[0129]

[Chemical 33]

The 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.

[0131]

[Table 19]

[0132]

[Table 20]

After washing with water and desalting (the compound represented by the precipitating agent (1) was used 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.

[0134]

[Table 21]

[0135]

[Chemical 34]

Next, a method for preparing a gelatin dispersion of a 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 the high boiling point solvent (2) were weighed, 70 ml of ethyl acetate was added, and the mixture was heated and dissolved 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 stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of the magenta dye-donor compound. The anionic surfactant (2) and high boiling point solvent (2) are the same as the corresponding compounds used in Example 1.

[0137]

[Chemical 35]

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 called a cyan dye-donor compound dispersion.

[0139]

[Chemical 36]

Yellow dye-donor compound (1) 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 called a yellow dye-donor compound dispersion.

[0141]

[Chemical 37]

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

[0143]

[Table 22]

[0144]

[Table 23]

[0145]

[Chemical 38]

[0146]

[Chemical Formula 39]

[0147]

[Chemical 40]

[0148]

[Chemical 41]

[0149]

[Chemical 42]

The anionic surfactant (1),
(2), (3), the water-soluble polymer (1), the high boiling point solvent (2), and the hardener (1) are the same as the corresponding compounds described in the photosensitive material of Example 1, respectively. 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 were each added to a 4% gelatin aqueous solution 10
In addition to 0 ml, the mixture was crushed for 30 minutes using glass beads having an average particle size of 0.75 mm in a mill. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, an image receiving material 201 having the constitution shown in Table C was prepared. Next, the image receiving material 20 was used except that the amount of the compound of the comparison and the compound of the present invention shown in Table G was added to the third layer.
Image-receiving materials 202 to 215 were prepared in the same manner as in No. 1.

[0152]

[Table 24]

[0153]

[Chemical 43]

The other compounds are the same as the corresponding compounds described in the image receiving material of Example 1.

Evaluation was carried out by the following exposure and processing.
The image-receiving material 20 produced in the above-mentioned photosensitive material and Example 1.
1 to 215 were used to perform exposure under the conditions shown in Table 23 using the laser exposure apparatus described in Japanese Patent Application Nos. 63-281418 and 63-204805. Exposed photosensitive material 2
Fountain solution was supplied to the 01 emulsion surface with a wire bar, and then the emulsion was superposed so that the image receiving material and the film surface were in contact with each other.
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 83 ° C., and an image was obtained on the image receiving material.

[0156]

[Table 25]

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

[0158]

[Table 26]

From Table H, the image receiving material 203 using the present invention is shown.
From No. 215, the maximum concentration is higher than the image receiving material 201 using nothing and the image receiving material 202 using the comparative compound, which shows that the compound of the present invention is effective.

Example 3 Image Receiving Material 30 of Table D in place of Image Receiving Material 201 of Example 2
1 and using the compound of the present invention in the third layer of 301,
When image-receiving materials 303 to 315 were prepared and the light-sensitive material 201 of Example 2 was used and evaluated in the same manner, the same tendency results as in Example 2 were obtained.

[0161]

[Table 27]

Therefore, it can be seen that the compounds of the present invention are effective. The compounds used for the image receiving materials 301 to 315 are the same as the corresponding compounds described in the image receiving materials of Examples 1 and 2.

Claims (1)

[Claims] 1. A color diffusion having at least one dye-fixing layer on a support, and the dye-fixing layer or other layers containing a compound represented by the following general formula (1). A dye fixing element used in the transfer method. General formula (1)