JPH09281676A - Heat developable color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the color balance of a white part by incorporating a specified compd. SOLUTION: This color photosensitive material has three photosensitive silver halide emulsion layers different from one another in color sensitivity on the substrate and contains a compd. represented by the formula PWR-(Time)t - Dye besides a binder and a dye imparting compd. releasing a diffusible dye in accordance with silver development. In the formula, PWR is a group releasing -(Time)t -Dye when the compd. is reduced, Time is a group releasing Dye through succeeding reaction after release as -(Time)t -Dye, (t) is 0 or 1, Dye is a dye or its precursor and PWR may be a part corresponding to a part contg. an electron accepting center and an intramolecular nucleophilic substitution reaction center in a compd. releasing a photographic reagent by intramolecular nucleophilic substitution reaction after the compd. is reduced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat development diffusion transfer type color light-sensitive material, and more particularly to a heat development diffusion transfer type color light-sensitive material in which the color balance of a white portion in an image is improved. The improvement of the color balance of the white portion here means that the point (a, b) on the chromaticity diagram is close to the origin (0, 0) in the Lab value of the CIE color system.

[0002]

2. Description of the Related Art Photothermographic materials are known in the art, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Optics", Non-Silver Salt Photographs, 1982, pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, for example, US Pat. Nos. 3,761,270 and 4,221,240 disclose a method of forming a dye image by a coupling reaction between an oxidized form of a developing agent and a coupler. A method of forming a positive color image by a photosensitive silver dye bleaching method is described in U.S. Pat. No. 4,235,957.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137 and 4559290, JP-A-58-14
No. 9046, JP-A-60-133449 and 59-2
Nos. 18443, 61-238056, EP-A-220746A2, JP-A-87-6199, and EP-A-210660A2.

Many methods have been proposed for obtaining a positive color image by thermal development. For example, U.S. Pat. No. 4,559,290 discloses that a compound obtained by converting a so-called DRR compound into an oxidized form having no ability to emit a color image in the presence of a reducing agent or a precursor thereof is used. A method has been proposed in which a diffusible dye is released by being oxidized and reduced by a reducing agent remaining without being oxidized. EP-A-220746A and JP-A-87-6199 (Vol. 12, No. 22) describe an NX bond (X) as a compound that releases a diffusible dye by the same mechanism.
Represents an oxygen atom, a nitrogen atom or a sulfur atom), and a heat-developable color light-sensitive material using a compound which releases a diffusible dye by reductive cleavage.

Among these heat development methods, in the heat development diffusion transfer type color light-sensitive material utilizing a dye donating compound which releases a diffusible dye corresponding to silver development, the color balance of the white portion in the image is There was a problem that it was bad.
In order to solve this problem, a patent on a heat-developable color light-sensitive material containing a dye trapping agent and having an improved color balance in the white portion has been reported, but a satisfactory color balance in the white portion has not been obtained.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat development diffusion transfer type color light-sensitive material in which the color balance of the white portion is improved.

[0008]

The above object can be achieved by the following constitutions.

(1) At least a binder on the support,
In a heat development diffusion transfer type color light-sensitive material containing a dye-donor compound that releases a diffusible dye corresponding to silver development, and three light-sensitive silver halide emulsion layers having different color sensitivities,
A heat-development diffusion transfer type color light-sensitive material comprising at least one compound represented by the following general formula (I). General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced by-(Time)
Represents a group that releases _t- Dye. Time is-(Ti
me) represents a group that is released as _t- Dye and then releases Dye via a subsequent reaction. t represents an integer of 0 or 1. Dye represents a dye or its precursor.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The compound represented by formula (I) will be described in more detail. First, the PWR will be described in detail. PWR is US Pat. No. 4,139,389 or US Pat. Nos. 4,139,379 and 4,564,577.
And JP-A-59-185333 and 57-84453.
As disclosed in US Pat. No. 6,989,984, which is equivalent to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after reduction. Good and US Patent 4,232,10
No. 7, JP-A-59-101649, Research Disclosure (1984) IV, 24025, or JP-A-61-88257, the photographic reagent is eliminated by an electron transfer reaction in the molecule after reduction. It may correspond to the electron-accepting quinonoid center in the compound to be released and the portion containing the carbon atom linking it to the photographic reagent. Also, JP-A-56-1425
30, US Pat. Nos. 4,343,893 and 4,61
No. 9,884, an aryl group substituted with an electron-withdrawing group in a compound that releases a photographic reagent by cleavage of a single bond after reduction and an atom (sulfur atom or carbon atom) connecting the aryl group and the photographic reagent. It may correspond to a portion containing an atom or a nitrogen atom). US Patent 4,4
No. 50,223, which may correspond to a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a moiety containing a carbon atom connecting the nitro group and the photographic reagent. U.S. Pat. No. 4,609,610
It may also correspond to the dieminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance as described in the above publication and the part containing the carbon atom connecting it to the photographic reagent. In addition, as more preferable ones, European Patent No. 220,746A2 and Open Technical Report 87-
6199, US Pat. No. 4,783,396, JP-A-6
Compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, as described in JP-A Nos. 3-201653 and 63-201654, and the like.
No. 26842, a compound having SO ₂ —X (where X has the same meaning as above) and an electron-withdrawing group in one molecule, JP-A-6-62
A compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-3-271344;
C-in one molecule described in JP-A-63-271341
X 'bond (X' is X as defined either or -SO ₂ - represents a)
And a compound having an electron-withdrawing group. Further, compounds described in JP-A-1-161237 and JP-A-1-161335, 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. In order to more fully achieve the object of the present invention, among the compounds of general formula [I], those represented by general formula [II] are preferable. General formula (II)

[0011]

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(Time)-_tDye is R¹⁰¹, R¹⁰²
Alternatively it binds to one of the EAGs. X is an oxygen atom (-O
-), A sulfur atom (-S-), a group containing a nitrogen atom (-N)
(R ¹⁰³)-) Is represented. R¹⁰¹, R¹⁰²And R¹⁰³Is
It represents a group other than a hydrogen atom or a mere bond. R¹⁰¹,
R¹⁰²And R¹⁰³As a group other than a hydrogen atom represented by
Include alkyl groups, aralkyl groups, alkenyl groups, and alkyl groups.
Nyl group, aryl group, heterocyclic group, sulfonyl group, carba
There are moyl group, sulfamoyl group, etc.
It may have a group. R¹⁰¹And R¹⁰³Is replaced or
Is an unsubstituted alkyl group, alkenyl group, alkynyl group,
Aryl group, heterocyclic group, acyl group, sulfonyl group, etc.
Is preferred. R ¹⁰¹, And R¹⁰³Has 1 to 40 carbon atoms
Is preferred. R¹⁰²Is a substituted or unsubstituted acyl group,
A sulfonyl group is preferred. An example is R¹⁰¹, R¹⁰³of
It is the same as the acyl group and sulfonyl group described at the time. carbon
The number is preferably 1-40. R¹⁰¹, R¹⁰²And R¹⁰³Is
They may combine with each other to form a 5- to 8-membered ring. X
Particularly preferred is an enzyme. Is EAG a reducing substance?
Represents a group that accepts an electron from another group, and is bonded to a nitrogen atom. EA
As G, a group represented by the following general formula [A] is preferable. General formula [A]

[0013]

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In the general formula [A], Sub is selected so that the sum of Hammett's substituent constants sigmapara of the substituents is +0.50 or more, more preferably +0.70 or more, and most preferably +0.85 or more. EAG is preferably an aryl group substituted with at least one electron-withdrawing group, or a heterocyclic group. Substituents attached to the aryl group or heterocyclic group of EAG can be used to control the physical properties of the entire chemical. Examples of the physical properties of the entire compound include adjustment of electron acceptability, water-soluble property, oil-soluble property, diffusibility, sublimation property, melting point,
It can be used to control dispersibility in a binder such as gelatin, reactivity with a nucleophilic group, reactivity with an electrophilic group, and the like. Specific examples of EAG are described in EP 220 746 A2, pages 6-7. The compound represented by the general formula [II] has a function of cleaving the bond between N and X when EAG receives (reduces) an electron, and triggers it to release (Time) _t -Dye. Time is nitrogen-oxygen, nitrogen-
Using the cleavage of nitrogen or the nitrogen-sulfur bond as a scratch,
Represents a group that releases Dye via a subsequent reaction. Ti
Various groups represented by me are known, and for example, JP-A-61-61
-147244, page (5) -page (6), ibid. 61-236.
No. 549 (8)-(14), Japanese Patent Application No. 61-8862
The groups described on page 5 (36)-(44) are mentioned. D
The dye represented by ye includes an azo dye, an azomethine dye, an anthraquinone dye, a naphthoquinone dye, a styryl group, a nitro dye, a quinoline dye, a carbonyl dye, and a phthalocyanine dye. These dyes can also be used in the form of a temporarily short wave which can be multicolored during development. Specifically, EP76,492A, JP-A-59-16505
Dye disclosed in No. 4 can be used. The above general formula (I
The compound represented by the formula I] needs to be non-migrating in the photographic layer itself, and therefore EAG, R ¹⁰¹ , R
It is desirable to have a ballast group having 8 or more carbon atoms at the position of ¹⁰² , R ¹⁰³ or X (particularly the position of EAG). Typical specific examples of the reducible dye-donating compound used in the present invention are listed below, but the present invention is not limited to these and is described in European Patent Publication 220746A2, Published Technical Report 87-6199 and the like. The dye-providing compounds described above can also be used.

[0015]

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[0016]

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[0017]

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[0018]

[Chemical 6]

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

[Chemical 12]

Each of these compounds can be synthesized by the methods described in the patent specifications cited above.
The amount of the compound of the general formula (I) to be used depends on the extinction coefficient of the Dye portion, but is 0.05 to 5 mg / m ² , preferably 0.1.
Is in the range of ˜3 mg / m ² . The compounds of general formula (I) can be used alone or in combination of two or more.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having different spectral regions are used in combination. To use. In the present invention, a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is employed. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

In general, the light-sensitive layer containing a yellow dye-donor compound contains a halogenated emulsion (blue-sensitive emulsion) having a spectral sensitivity in the wavelength range of 400 to 500 nm and a magenta dye-donor compound. The photosensitive layer is
A halogenated emulsion spectrally sensitized to the range of 600 to 600 nm (green-sensitive emulsion) is similarly applied to a photosensitive layer containing a cyan dye-donating compound. Emulsion). In this case, since the yellow photosensitive layer is colored yellow, it is desirable that the yellow photosensitive layer is the uppermost photosensitive layer apart from the support.

That is, from the support, a cyan dye-donor compound-containing red-sensitive layer, an intermediate layer, a magenta dye-donor compound-containing green-sensitive layer, an intermediate layer, a yellow dye-donor compound-containing blue-sensitive layer, an intermediate layer and a protective layer. Is a union. The cyan layer and the magenta layer have almost the same characteristics even if they are reversed. Also, each photosensitive layer is
It consists of two layers, each of which may contain a dye-donating compound and a halide emulsion, or an upper layer containing a silver halide emulsion and a lower layer containing a dye-donating compound,
It is also possible to increase the sensitivity.

The heat development diffusion transfer type color light-sensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. When the support is polyethylene-laminated paper containing a white pigment such as titanium oxide, the back layer must be designed to have an antistatic function and have a surface resistivity of 10 ¹² Ω · cm or less. .

The silver halide emulsion used in the heat development diffusion transfer type color light-sensitive material of the present invention will be described in detail below.

The silver halide emulsion comprises silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide may be used. The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and is disclosed in JP-A-1-167,743,
As described in JP-A-223,463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm.
The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. Those having such twin defects, composites thereof, or any other materials may be used. Specifically, US Pat. No. 4,500,626, column 50, 4,628,021
No. 17, 029 (1978), Research Disclosure Magazine (hereinafter abbreviated as RD), No. 17,
643 (December 1978), pp. 22-23, No. 1
8, 716 (November 1979), p. 648, ibid.
07, 105 (November 1989) pp. 863-865,
JP-A Nos. 62-253,159 and 64-13,546.
JP-A-2-236546, 3-110,55
No. 5, Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemieet Phisique Photog)
raphique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Pho
tographic Emulsion Chemistry, Focal Press, 196
6), "Manufacture and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al., Making and C).
oating Photographic Emulsion, Focal Press, 196
Any of the silver halide emulsions prepared by the methods described in 4) and the like can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-4-126629 are preferably used.

The amount of iridium used in the present invention is preferably 10 ^-9 to 10 ^-4 mol, and more preferably 10 ^-8 to 10 ^-6 mol, per mol of silver halide. In the case of a core-shell emulsion, iridium may be added to the core and / or the shell. Compounds include K ₂ IrC
l ₆ and K ₃ IrCl ₆ is preferably used.

The addition amount of rhodium used in the present invention is preferably 10 ^-9 to 10 ^-6 mol per mol of silver halide.

Further, the preferable addition amount of iron used in the present invention
Is 10 per mole of silver halide ^-7-10^-3In moles
And more preferably 10^-6-10^-3Is a mole.

A part or all of these heavy metals is previously doped in a fine grain emulsion of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc., and then this fine grain emulsion is added to halogenate A method of locally doping the surface of the silver emulsion is also preferably used.

In the step of forming grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thioether compound or JP-B No. 47-1 is used.
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel., 1697), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al.
L. Zelikman et al., Making and Coating Photographic
Emulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can also be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and JP-A-55-158). 124, U.S. Pat. No. 3,650,757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to provide the photosensitive silver halide used in the present invention with blue, green and red sensitivities,
The photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. If necessary, the infrared sensitivity may be subjected to spectral sensitization. The dyes used include cyanine dyes,
Merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are included. Specifically, US Pat. No. 4,617,257,
JP-A Nos. 59-180,550 and 64-13,546.
And the sensitizing dyes described in JP-A Nos. 5-45,828 and 5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641 and those described in JP-A-63-23, 145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

Additives used in such steps and known photographic additives usable in the photothermographic material and dye fixing material of the present invention are described in RD No. 17,643,
It is described in No. 18,716 and No. 307,105, and the corresponding parts are summarized in the table below. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer ~ page 649 right column 4. Fluorescent brightener 24 page 648 page right column 868 5. Fog prevention 24 ~ 25 page 649 right column 868 ~ 870 agent, stabilizer 6. 26Page 26 649 Right column Page 873 Filter 左 Page 650 Left column Dye, UV absorber 7.Dye image 25 650 Page Left column 872 Stabilizer 8.Hardening agent 26 Page 651 Left column 874-875 9. Binder page 26 page 651 left column 873-874 10. plasticizer, page 27 650 page right column 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12 Static page 27 page 650 right column pages 876-877 Inhibitor 13. Matting agent pages 878-879

A hydrophilic binder is preferably used as the binder of the constituent layers of the photothermographic material and the dye fixing material. Examples thereof include the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75).
Page. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol,
Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also, U.S. Pat.
No. 0,681, JP-A-62-245260, etc., ie, -COOM or -SO
_A homopolymer of a vinyl monomer having 3M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (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 kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

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, more preferably 10 g or less, and further preferably 7 g to 0.5 g per 1 m ² .

In the present invention, an organic metal salt may be used as an oxidizing agent together with the light-sensitive silver halide emulsion. 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 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. U.S. Pat. No. 4,500,626 is an example of a reducing agent used in the present invention.
No. 49-50, No. 4,839,272, No. 4,
330,617, 4,590,152, 5,0
17,454, 5,139,919, JP-A-60
-140,335, pages (17)-(18), ibid. 57.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181, 742, No. 61-259, 253.
No. 62-201, 434, and No. 62-244, 04.
No. 4, 62-131, 253, 62-131, 62
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
No. 2-234, 158, 3-160, 443
And EP-A-220,746, pages 78 to 96, and the like. Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transferring agent may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Further, a method of stably introducing the compound into the layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols,
No. 110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, compounds described as electron donors, and a non-diffusible and reducing dye described later. Donor compounds and the like. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixture, improvement of color reproduction, improvement of white background, and prevention of silver transfer to dye fixing material. Specifically, European Patent Publication No. 52
4,649,357,040, JP-A-4-24
9,245, 2-64,633, 2-46,4
No. 50 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
And JP-A-2-64,634, JP-A-3-43,735, and EP-A-451,833. In the present invention, the total amount of the reducing agent is 0.01 to 20 mol per mol of silver,
Particularly preferably, it is 0.1 to 10 mol.

In the present invention, silver ions are reduced to silver.
Compound that releases diffusible dye in response to this reaction
That is, a dye-providing compound is used. Dye donating
Function to release diffusible dye imagewise as an example of compound
A compound having This type of compound
It can be represented by the following general formula [LI]. ((Dye ')_m-Y)_n-Z [LI] Dye 'is a dye group or dye represented by the general formula (II).
Dye groups other than precursor groups, dye groups that have been temporarily shortened,
Or Y represents a dye precursor group, and Y is a simple bond or linking group.
Represents Z, and Z corresponds to a photosensitive silver salt having an image-wise latent image
((Dye ') _m-Y)_nExpansion of compounds represented by -Z
Difference in dispersiveness, or (Dye ')_m-Y
Released and released (Dye ′)_m-Y and ((Dy
e ')_m-Y)_n-Differences in diffusivity from Z
Represents a group having the following property, and m is an integer of 1 to 5
Represents a number, n represents 1 or 2, and either m or n is
When not 1, the plural Dye's may be the same or different.
Good. More specifically, they are the following compounds.

A coupler having a diffusible dye as a leaving group, which is a non-diffusible compound itself (DDR coupler) which releases a diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-
39,165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 4,483,914. Is reducible to silver halides or organic silver salts,
It itself is a non-diffusible compound (DRR compound) that releases a diffusible dye when it reduces the other party. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322 and JP-A-56-65,839. 59-69,839, 53-3,819, 51-104,343, RD
17,465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116,537, 57-179,840.
And U.S. Pat. No. 4,500,626. 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), (2
8) to (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, Nos. 37-3
The compounds described in column 9 are also useful. In addition, as a dye-donor compound other than the above-mentioned coupler and the general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, 54-).
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, etc.), leuco dyes (US Patent No. 3,985,565,
No. 4,022,617, etc.) can also be used. In the present invention, this DRR compound is particularly preferably used. The amount of the DRR compound added is yellow, magenta,
0.01 g / m ^{2 to} 3 g / of each compound of cyan
Used in the m ² range. More preferably, 0.03 g /
It is used in the range of m ^{2 to 1} g / m ² .

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layer of the photothermographic material by known methods such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
Nos. 55,470, 4,536,466, 4,53
6,467, 4,587,206, 4,55
No. 5,476, No. 4,599,296, Japanese Examined Patent Publication 3-6
A high-boiling point organic solvent such as that described in No. 2,256 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. Also, 1 cc or less per 1 g of binder, further 0.5 cc
Below, especially 0.3cc or less is suitable. In addition, Tokiko Sho 51
-39,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,287.
No. 42 or the like and a method of adding it as a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No.
The surfactants described in Research Disclosure, pages 7 to 38, mentioned above, can be used. In the photothermographic material of the present invention, a compound capable of activating development and stabilizing an image at the same time can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, for the purpose of improving the white background of the obtained image by immobilizing or achromating unnecessary dyes and coloring matters in the constituent layers of the photothermographic material of the present invention. Various compounds can be added. Specifically, European Published Patent No. 353,741
No. 461,416, JP-A-63-163,345.
And the compounds described in JP-A Nos. 62-203,158 can be used.

Various pigments and dyes can be used in the constituent layers of the photothermographic material of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure and European Published Patent No. 479,1
67, No. 502,508, JP-A-1-167,83
No. 8, No. 4-343, 355, No. 2-168, 252
No. 6, JP-A-61-20,943, European Published Patent No. 47
The compounds and layer constitutions described in No. 9,167, No. 502,508 and the like can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photothermographic material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye fixing material, 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 invention. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88,256, pages (32) to (41),
Mordants described in U.S. Pat. Nos. 4,774,162 and 4,619,883.
And Nos. 4,594,308 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The hydrophilic binder is preferable as the binder used in the dye fixing material of the present invention. Further, it is preferable to use carrageenans as described in EP-A-443,529 and latexes having a glass transition temperature of 40 ° C. or lower as described in JP-B-3-74,820. Auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided on the dye fixing material as needed. It is particularly useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye fixing material, a high boiling point organic solvent can be used as a plasticizer, a slipping agent or an agent for improving the releasability between the photosensitive material and the dye fixing material. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. As examples thereof, various modified silicone oils, particularly carboxy-modified silicone (trade name: X-22-3710) described in “Modified Silicone Oil” Technical Documents P6 to 18B issued by Shin-Etsu Silicone Co., Ltd. are effective. Silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.

An anti-fading agent may be used in the photothermographic material and the dye fixing material. Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes. Dye image stabilizers and ultraviolet absorbers described in Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61
The compounds described in -159,644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681), and benzophenone-based compounds (Japanese Unexamined Patent Publication No. 2,784), and JP-A Nos. 54-48,535 and 62-1.
36, 641 and 61-88, 256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3-36, No. 4,254,195, No. 3
Columns 8 to 8, JP-A-62-174,741 and JP-A-61-8
8, 256, pp. 27-29, pp. 63-199,
No. 248, JP-A Nos. 1-75,568 and 1-74,2
No. 72 and the like.

The anti-fading agent for preventing the fading of the dye transferred to the dye fixing material may be contained in the dye fixing material in advance, or the dye may be externally applied from the photothermographic material or a transfer solvent described later. You may make it supply to a fixing material. The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination. A fluorescent whitening agent may be used in the photothermographic material or the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photothermographic material or a transfer solvent. For example, see “The Chemis” edited by K. Veenkataraman.
tryof Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers, and fluorescent whitening agents are described in JP-A-62-21527.
No. 2, pages 125 to 137, JP-A-1-161,
No. 36, pages (17) to (43).

As the hardener used in the constituent layers of the photothermographic material and the dye fixing material, the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, US Pat. Sho 59-116,655
Nos. 62-245,261 and 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.),
N-methylol hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be used. These hardeners are
0.001 to 1 g, preferably 0.005 to 0.5 g, is used per 1 g of gelatin applied. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the photothermographic material and dye fixing material. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-62-13546 (7). Pages (9), (57) to (71) and (8)
1) to (97), U.S. Pat. No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No. 63-264,747, JP-A-1-150,1.
No. 35, No. 2-110, 557, No. 2-178, 65
No. 0, RD 17, 643 (1978) (24)-(2
5) Compounds described on page and the like. These compounds are preferably used in an amount of 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

In the constituent layers of the photothermographic material and the dye fixing material, coating aids, improving releasability, improving slipperiness, antistatic,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in the aforementioned Research Disclosure, JP-A-62-173463, and JP-A-62-173463.
183,457. The constituent layers of the photothermographic material and the dye-fixing material 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-61-209 can be used.
No. 44, No. 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photothermographic material and the dye fixing material for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin and polymethacrylate, and JP-A-63-2747 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
Nos. 44 and 63-274952.
In addition, the compounds described in the above Research Disclosure can be used. These matting agents are the top layer (protective layer)
In addition, it can be added to the lower layer as needed.
In addition, the constituent layers of the photothermographic material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32),
No. 11,338 and Japanese Patent Publication No. 2-51,496.

In the present invention, an image forming accelerator can be used in the photothermographic material and / or dye fixing material. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the formation of a dye from a dye-providing substance or the decomposition of a dye or the release of a diffusible dye, and the development of a photothermographic material. It has the function of promoting the transfer of dye from the material layer to the dye fixing layer, and from the physicochemical function, bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants , Silver, or compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. An example is U.S. Pat.
Nos. 514,493 and 4,657,848.

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, a method of incorporating a base and / or a base precursor in a dye fixing material is preferable from the viewpoint of enhancing the storability of the photothermographic material. . In addition to the above,
EP 210,660, U.S. Pat. No. 4,74
No. 0,445, a 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), and JP-A-61-232451. The compounds that generate a base by electrolysis described in 1) can also be used as the base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the photothermographic material and the dye-fixing element, as described in the aforementioned patent.

In the present invention, various development terminators can be used in the photothermographic material and / or the dye fixing material for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. . The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For more details, see
2-253, 159, pages (31) to (32).

In the present invention, the support for the photothermographic material or dye fixing material is one that can withstand the processing temperature. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver halide photography-", pages 223 to 240, published by Corona Co., Ltd. (1979). And photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further, Film-processed synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as required. In addition, JP-A-62-253,159, pages (29) to (31), JP-A-1-161,236, pages (14) to (17), and JP-A-63-316,848.
JP-A-2-22,651, JP-A-3-56,955
No. 5,001,033 and the like can be used. The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent. Specifically, JP-A-63-22024
No. 6, etc. can be used. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

As a method of exposing and recording an image on the photothermographic material, for example, a method of directly photographing a landscape or a person by using a camera, or a method of exposing through a reversal film or a negative film by using a printer or an enlarger is used. Method, scanning exposure of the original image through a slit, etc. using an exposure device of a copying machine, scanning exposure by causing image information to emit light through a light emitting diode, various lasers (laser diode, gas laser, etc.) Method (Japanese Patent Application Laid-Open No. 2-129,625, Japanese Patent Application No. 3-33)
8,182, 4-9,388, 4-281,4
No. 42 etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., and exposing directly or via an optical system.

As a light source for recording an image on the photothermographic material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., US Pat. No. 4,500,626, column 56, Special Features Kaihei 2-53,
No. 378 and 2-54,672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KDP). ), Lithium iodate, BaB ₂ O _{4 and the} like, and urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462 and JP-A-62-2104
The compound described in No. 32 is preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTT).
SC), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created using a computer such as CG and CAD can be used.

The photothermographic material and / or dye fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is described in JP-A-61-14.
No. 5,544 and the like can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and particularly about 60 ° C. to 180 ° C. is useful. The dye 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 transfer temperature can be in the range from the temperature in the thermal development step to the room temperature, but is particularly 50 ° C. or higher, and is about 10 ° C. lower than the temperature in the thermal development step.
Up to lower temperatures are preferred.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this system, 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. to 100 ° C. Examples of the solvent used for accelerating the development and / or for diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the section of the image formation accelerator). Described are used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up, or may be circulated and repeatedly used. In the latter case, water containing components eluted from the material will be used. Further, JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
The device described in No. 5, etc. or water may be used.

These solvents can be applied to the photothermographic material, the dye fixing material or both of them. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of giving this water,
For example, the methods described in JP-A-62-253,159 (page 5) and JP-A-63-85,544 are preferably used. In addition, the solvent is enclosed in the microcapsule,
It can also be used in the form of a hydrate incorporated in advance in the photothermographic material or the dye fixing element or both. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

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 photothermographic material and / or the dye fixing material can also be adopted. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

The heating method in the development and / or transfer step includes contacting with a heated block or plate, heating plate, hot presser, heating roller, heating drum, halogen lamp heater, infrared and far infrared lamp heater. For example, or by passing through a high-temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application Nos. 4-277,517 and 4
Devices described in JP-A-243,072 and JP-A-4-244,693 are preferably used. Further, as a commercially available apparatus, a Pictrostat 100, a Pictrostat 200, a Pictography 3000, a Pictography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

[0074]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example Method of Making Light-Sensitive Silver Halide Emulsion Light-Sensitive Silver Halide Emulsion (1) [for red-sensitive emulsion layer] Well stirred gelatin aqueous solution (800 g of gelatin and potassium bromide in 26.3 liters of water) 53 g by adding 12 g, 80 g of sodium chloride and 1.2 g of compound (a)
Solution (Table 1) was added at an equal flow rate for 9 minutes, and solution (II) was added 9 seconds from 10 seconds before the addition of solution (I).
Added at an equal flow rate for 10 minutes. After 6 minutes, (II in Table 1
Solution (I) was added at a constant flow rate for 24 minutes, and solution (IV) was added simultaneously with solution (III) at the same flow rate for 24 minutes and 30 seconds. After washing with water and desalting (performed with a precipitating agent (a) at pH 4.0) by a conventional method, 880 g of lime-treated ossein gelatin and 2.8 g of compound (b) were added to bring the pH to 6.0. After adjustment, 12.8 g of a ribonucleic acid degradation product and 32 mg of trimethylthiourea were added, and optimal chemical sensitization was performed at 60 ° C. for 71 minutes, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.2. 6 g, 3.2 g of the dye (a), 5.1 g of KBr, and 2.6 g of a stabilizer described later were sequentially added, and then cooled. Thus, 28.1 kg of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.32 μm was obtained.

[0076]

[Table 1]

[0077]

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Photosensitive Silver Halide Emulsion (2) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 2 g of sodium chloride in 600 ml of water).
g) and 30 mg of compound (a) were added, and the mixture was kept at 46 ° C.). Solution (I) and solution (II) in Table 2 were simultaneously added at an equal flow rate for 9 minutes. After 5 minutes, the liquid (III) and the liquid (IV) shown in Table 2 were further added.
The solution was added simultaneously at an equal flow rate for 32 minutes. Also, 11 minutes after the addition of the (III) solution, 100% of a 1% aqueous solution of potassium iodide was added.
cc was added. Further, 1 minute after the addition of the solutions (III) and (IV) was completed, 60 ml of a methanol solution of the dye (containing 360 mg of the dye (b1) and 73.4 mg of the dye (b2)) was added all at once. Washing with water and desalting by a conventional method (pH using the precipitation agent (a)
Calcium-treated ossein gelatin 22)
g, pH and 6.0 are adjusted to 6.0 and 7.6 by adding appropriate amounts of NaCl and NaOH, 0.18 g of ribonucleic acid degradation product, 4.2 mg of sodium thiosulfate, and 4-hydroxy-6-methyl are added. 180 mg of -1,3,3a, 7 tetrazaindene was added and optimum chemical sensitization was performed at 60 ° C, and then 90 mg of the antifoggant (1) was added, followed by cooling. In addition, 70 mg of compound (b) and 3 of compound (c) were used as preservatives.
ml was added. Thus, the average particle size is 0.30μ
635 g of a monodisperse cubic silver chlorobromide emulsion of m were obtained.

[0079]

[Table 2]

[0080]

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[0081]

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Photosensitive silver halide emulsion (3) [for blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (1582 g of gelatin, 127 g of KBr and 660 mg of compound (a) were added to 29.2 liters of water, and the mixture was heated to 72 ° C). The liquids I and II having the compositions shown in Table 3 were added to the liquids that were kept), and after 10 seconds, I was added.
The liquid was added over 30 minutes each. In addition, 2 minutes after the addition of the solution I, the solution V was added, and 5 minutes after the addition of the solution II, the IV solution was added.
The solution was added, and 10 seconds after that, the solution III was added over 27 minutes and 50 seconds for the solution III and for 28 minutes for the solution IV.

Then, after washing with water and desalting in a conventional manner (using 32.4 g of a precipitating agent (b) at pH 3.9), 1230 g of lime-treated ossein gelatin and 2.8 mg of compound (b) were added. PH 6.1, pAg 8.4
According to. Then, 24.9 mg of sodium thiosulfate
In addition, after optimal chemical sensitization at 65 ° C. for about 70 minutes, 13.1 g of the dye (c) and 118 ml of the compound (c) were sequentially added, followed by cooling. The silver halide grains of the obtained emulsion were potato-like grains, the grain size was 0.53 μm, and the yield was 3
It was 0.7 kg.

[0084]

[Table 3]

[0085]

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Next, a method for preparing a gelatin dispersion of the compound (d) will be described. 0.4 g of the compound (d), 1.2 g of the high-boiling organic solvent (1), 0.12 g of the compound (f),
0.25 g of compound (g) and 0.05 of compound (h)
g, 0.2 g of surfactant (1), 9.5 cc of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to form a uniform solution. This solution and an 18% solution of lime-processed gelatin 29.1
g, and then mixed with a homogenizer for 100 minutes for 10 minutes.
Dispersed at 00 rpm. After dispersion, add 18.5 cc of water for dilution.
added. This dispersion is referred to as a dispersion of the compound (d).

[0087]

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A method for preparing a zinc hydroxide dispersion will be described. Zinc hydroxide 12.5 having an average particle size of 0.2 μm
g, 1 g of carboxymethylcellulose as a dispersant, 0.1 g of sodium polyacrylate in a 4% aqueous gelatin solution 10
In addition to 0 ml, the mixture was milled 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 dispersion of zinc hydroxide.

A method for adjusting the dye trapping agent will be described.
While stirring 108 cc of polymer latex A1 (solid content 13%), pH of 10% aqueous solution of surfactant (SF1) was added.
Until 6.5 was reached. The suspension thus obtained was concentrated to 500 cc using an ultrafiltration module, desalted, 1500 cc of water was added, and the same operation was repeated once again. This liquid is called a dye trap agent.

[0090]

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Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Cyan dye-donating compound (A
1) 7.3 g, cyan dye-donating compound (A2) 11.0 g, surfactant (1) 0.8 g, compound (h) 1 g, compound (i) 2.2 g, high boiling point 7 g of the organic solvent (1) and 3 g of the high boiling organic solvent (2) are weighed,
Ethyl acetate (26 ml) and water (1.2 ml) were added and dissolved by heating at about 60 ° C. to form a uniform solution. This solution, 65 g of a 16% solution of lime-processed gelatin, and 87 cc of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. After dispersion, 216 cc of water for dilution was added. This dispersion is referred to as a dispersion of a cyan dye-donating compound.

[0092]

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[0093]

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3. The magenta dye-donor compound (B) was used.
57 g, compound (m) 0.051 g, compound (h) 0.051 g, compound (h) 0.032 g, surfactant (1) 0.094 g, high boiling organic solvent (2) 2.
3 g was weighed, 12 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 15.4 g of a 16% solution of lime-processed gelatin and 23.7 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After that, 43 cc of dilution water was added. This dispersion is referred to as a dispersion of a magenta dye-donating compound.

[0095]

[Chemical 21]

The yellow dye-donor compound (C) was added to
g, 2.3 g of compound (d) and 0.9 g of compound (h)
g, 0.88 g of surfactant (1), 3.9 g of compound (J), 1.9 g of compound (K), and 16.9 g of high boiling organic solvent (1), and 49 ml of ethyl acetate was added. ,
The mixture was dissolved by heating at about 60 ° C. to form a uniform solution. This solution, 63.5 g of a 16% solution of lime-processed gelatin and 103 cc of water
After stirring, mix with a homogenizer for 10 minutes at 10,000
Dispersed at rpm. Thereafter, 94 cc of water for dilution was added. This dispersion is referred to as a yellow dye-donating compound dispersion.

[0097]

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From these, the photothermographic materials 101 shown in Table 4, Table 5, Table 6 and Table 7 were constructed.

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

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[0104]

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Next, how to make the image receiving material will be described. An image receiving material R201 having a constitution as shown in Tables 8 and 9 was prepared.

[0106]

[Table 8]

[0107]

[Table 9]

[0108]

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[0109]

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Next, a method for preparing a gelatin dispersion containing the compound of the present invention will be described. The compound (2) of the present invention was added to 0.
018 g, compound (o) 0.0089 g, compound (d) 0.4 g, high boiling organic solvent (1) 1.2 g,
0.12 g of compound (f) and 0.25 of compound (g)
g, 0.053 g of compound (h), 0.25 g of surfactant (1), 5.3 cc of ethyl acetate was added,
It was heated and dissolved at ℃ to obtain a uniform solution. After stirring and mixing this solution with 62.5 g of a 16% solution of lime-processed gelatin,
Disperse with a homogenizer at 10,000 rpm for 10 minutes. After the dispersion, 132 cc of water for dilution was added. This dispersion is referred to as a gelatin dispersion of the compound (2) of the present invention.

[0111]

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A light-sensitive material 102 was prepared in the same manner as in the light-sensitive material 101 except that the gelatin dispersion of the second layer was changed to the gelatin dispersion of the present invention.

Next, the light-sensitive materials 101 to 102 were subjected to the following exposure and processing. Using a tungsten light bulb, through an equivalent neutral density filter whose density is continuously changing and a CC filter for color correction manufactured by Fuji Photo Film Co., Ltd.
It was exposed for / 10 seconds. Fountain solution was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the layers were superposed so that the image receiving material 201 and the film surface were in contact with each other. After heating at a heat development temperature of 83 ° C. for 30 seconds, the image receiving material was peeled off from the photosensitive material to obtain an image on the image receiving material. Table 10 shows the results of measuring the white part of the obtained image with a color difference meter CR-200 manufactured by Minolta Camera Co., Ltd. As is clear from this result, the light-sensitive material of the present invention is
It can be seen that it is closer to white and the color balance is improved.

[0114]

[Table 10]

Further, the light-sensitive material and the image-receiving material of the present invention were processed into a roll type and manufactured by Fuji Photo Film Co., Ltd. in 1994.
It was set on the Fujix Pictrostat 330, which was released in Japan from December of 2012. Also, Fujicolor Super G
Set the processed negative of 400ACE in the slide enlarging unit (NSE330),
All of the water application conditions, transport conditions, exposure control, etc. were performed under the standard conditions of the Fujix Pictrostat 330. Printed images from the negatives were obtained with all of the light-sensitive materials, but particularly with the light-sensitive materials of the present invention, images with even better image quality were obtained. Also, Fujicolor Super G400AC
G100ACE other than E and Eastman Kodak Su
Even with negatives such as per Gold 100/200/400, excellent images were obtained with the light-sensitive material of the present invention.

Claims (1)

[Claims] 1. A heat comprising at least a binder, a dye-donor compound releasing a diffusible dye corresponding to silver development, and three light-sensitive silver halide emulsion layers having different color sensitivities on a support. A development diffusion transfer type color light-sensitive material, comprising at least one compound represented by the following general formula (I), a heat development diffusion transfer type color light-sensitive material. General formula (I) PWR- (Time) _t -Dye In the formula, PWR is reduced by-(Time)
Represents a group that releases _t- Dye. Time is-(Ti
me) represents a group that is released as _t- Dye and then releases Dye via a subsequent reaction. t represents an integer of 0 or 1. Dye represents a dye or its precursor.