JP3231507B2 - Photothermographic materials and dye fixing materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable light-sensitive material containing a light-sensitive silver halide (hereinafter also referred to as "photosensitive material"). It is about materials.

[0002]

2. Description of the Related Art Photothermographic materials are known in the art, and photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-Silver Salt Photo Edition (Corona Co., 1992).
1982), pages 242 to 255, U.S. Pat.
0,626 and the like. Many methods have been proposed for obtaining a color image by thermal development.
For example, U.S. Patent Nos. 3,531,286 and 376,127.
No. 0, No. 4021240, Belgian Patent No. 80251
No. 9, Research Disclosure Magazine (hereinafter abbreviated as RD), September 31, 1975, pages 31 to 32, etc., have proposed a method of forming a color image by combining an oxidized form of a developing agent with a coupler.

However, since the heat-developable photosensitive material for obtaining the above-mentioned color image is a non-fixing type, silver halide remains even after image formation, and when exposed to strong light or stored for a long time, a white background gradually becomes colored. A serious problem.
Furthermore, the above-mentioned methods generally have a disadvantage that development takes a relatively long time, and the obtained image can only obtain high fog and low image density.

[0004] In order to improve these disadvantages, a diffusible dye is formed or released imagewise by heating, and the diffusible dye is transferred to an image receiving material (dye fixing material) having a mordant with a solvent such as water. (US Pat. Nos. 4,500,626 and 4,483,914;
No. 4,559,920, JP-A-59-165054, etc.).

In the above method, the developing temperature is still high, and the temporal stability of the photosensitive material is not sufficient. Therefore, Japanese Patent Application Laid-Open No. SHO 59-59 discloses a method in which heat development is performed in the presence of a base or a base precursor and a trace amount of water to transfer the dye, thereby accelerating the development, lowering the development temperature, and simplifying the processing.
-218443, 61-238056, 62-
187341 and EP210660A2.

In the method of forming an image by transferring such a movable dye, the diffusivity of a compound having a diffusibility other than the dye is also increased, so that an image is formed and / or It has been found that stains occur on the dye-fixing material during storage, particularly during image storage.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material and a dye-fixing material having less stain, without lowering the image density.

[0008]

The object of the present invention has been attained by a photothermographic material and a dye fixing material having the following constitutions. At least a photosensitive silver halide emulsion on a support,
A photothermographic material comprising a binder and a dye-donating compound, comprising at least one compound represented by the following general formula (1).

[0009]

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[0010] In the general formula (1), each independently R ₁ and R ₂ represents an aromatic hydrocarbon group or heterocyclic group may have one or more substituents, respectively. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a lower alkyl group. m _{1 to} m ₆ each independently represent an integer of 1 . n represents an integer of 0 or 1, k and j each represent an integer of 0 to 4, k + j is 1 or more, and n + k + j is an integer of 1 to 4. A represents an n + k + j-valent group, and n + k + j =
In the case of 2, A may be a single bond.

In a dye-fixing material having at least a binder and a mordant on a support, the following general formula (1)
A dye-fixing material comprising at least one compound represented by the formula:

[0012]

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[0013] In the general formula (1), each independently R ₁ and R ₂ represents an aromatic hydrocarbon group or heterocyclic group may have one or more substituents, respectively. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a lower alkyl group. m _{1 to} m ₆ each independently represent an integer of 1 . n represents an integer of 0 or 1, k and j each represent an integer of 0 to 4, k + j is 1 or more, and n + k + j is an integer of 1 to 4. A represents an n + k + j-valent group, and n + k + j =
In the case of 2, A may be a single bond.

[0014]

[Specific constitution] The compound represented by formula (1) used in the photothermographic material and the dye fixing material of the present invention will be described in more detail. In the formula (1), R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a lower alkyl group (eg, methyl, ethyl, propyl, butyl, etc.);
It preferably represents a hydrogen atom. m _{1 to} m ₆ each independently represent an integer of 1 . n represents an integer of 0 or 1, and k and j
Represents an integer of 0 to 4, k + j is 1 or more, and n +
k + j is an integer from 1 to 4. A represents an n + k + j-valent group, and when n + k + j = 2, A may be a single bond.
A more specifically represents a hydrogen atom, an alkyl group, an aryl group or the like in the case of a monovalent group, and represents a single bond,-(CH ₂ ) _d- (where d is 1 to ₃ ) in the case of a divalent group. An arylene group (e.g., 1,2-, 1,3-,
1,4-phenylene group), and in the case of a trivalent group, s
ym-triazine group (that is, 1,3,5-triazine-
2,4,6-triyl group) and the like. R ₁ and R ₂ each independently represent an aromatic hydrocarbon group or heterocyclic group may have one or more substituents, respectively.

R ₁ and R ₂ are preferably represented by the following general formula (2)
Or a substituent represented by (3).

[0016]

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In the general formula (2), R ₁₁ represents an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group or an aryl group. Each of these groups may further have one or more substituents. Examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an amino group, an N-substituted amino group, and an acylamino group. Carbamoyl group, N-substituted carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, N-substituted sulfamoyl group, cyano group, hydroxyl group, nitro group, halogen atom and the like. Can be The total number of carbon atoms contained in R ₁₁ is preferably 1 to 40. Among these, preferred substituents are an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a sulfonylamino group, and a halogen atom. p represents an integer of 0 to 5, and when p is 2 or more, a plurality of R ₁₁ may be the same or different.

[0018]

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In the above general formula (3), Q represents an oxygen atom, a sulfur atom or an —N (R ₂₁ ) — group (R ₂₁ represents a hydrogen atom, an alkyl group, an unsaturated alkyl group, or a substituted or unsubstituted aryl group, respectively) Or an aralkyl group). Y represents —C (R ₁₂ ) = or a nitrogen atom (−
N =). G represents —C (R ₁₃ ) = or a nitrogen atom (−
N =). R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group (preferably having a total of 1 to 40 carbon atoms),
Unsaturated alkyl group, a substituted or unsubstituted aryl group or aralkyl group, -SR ₂₂ group (R ₂₂ is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, carboxylic acid group or an alkali metal salt or alkylsulfonic acid, A group or an alkali metal salt thereof), or —NHR ₂₂ (R ₂₂ is as defined above). Y is -C
When (R ₁₂ ) = and G is -C (R ₁₃ ) =, R ₁₂
And R ₁₃ may combine to form a substituted or unsubstituted aromatic carbocycle or nitrogen-containing heterocycle.

Among the substituents represented by the general formula (3), particularly preferred are the substituents represented by the following general formulas (3-1), (3-2) or (3-3).

[0021]

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In the general formulas (3-1) and (3-2), R ₁₄ has the same meaning as R ₁₁ described above, and q represents an integer of 1 or 2. When q is 2, two R ₁₄ may be the same or different. Q represents a sulfur atom or a —N (R ₂₁ ) — group (R ₂₁ is as defined above). In the general formula (3-3), Z represents a —SR ₁₅ group or a —NHR ₁₆ group.
R ₁₅ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkylcarboxylic acid group or an alkali metal salt thereof, or an alkylsulfonic acid group or an alkali metal salt thereof. R ₁₆ has the same meaning as R ₁₅ .

Hereinafter, the general formula (1) used in the present invention will be described.
Preferred specific examples of the compound represented by are shown below, but it should not be construed that the invention is limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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In the present invention, the compound represented by the general formula (1) is usually used in a range of 10 ^-5 to 10 ^-1 equivalent in terms of a functional group represented by -S- per equivalent of the total coated silver amount. , Preferably in the range of 10 ^-4 to 10 ^-2 equivalents.

When the hydrophobic compound of the formula (1) of the present invention is dissolved in an organic solvent immiscible with water, it may be dissolved in this organic solvent, emulsified and dispersed, and added. And Japanese Patent Application Laid-Open Nos. Sho 59-174830 and
It may be added as a fine particle dispersion prepared by the method described in 102733 and the like.

In the present invention, the added layer of the compound represented by the general formula (1) includes a photosensitive layer, an intermediate layer, a protective layer, etc. of a photosensitive material, and an undercoat layer, a mordant layer, and an intermediate layer of a dye fixing material. Or a protective layer. In the case of a photosensitive material, it is preferable to add it to the protective layer. In the invention, even when the compound of the general formula (1) is added to the layer of the photothermographic material, the compound is diffused and transferred to the dye-fixing material together with the dye-providing compound during the heat development. Therefore, stains that tend to occur on the dye-fixing material during image storage after thermal development can be effectively prevented.

The photothermographic material used in the present invention basically comprises a support having thereon a photosensitive silver halide, a binder, a dye-donating compound (which may also serve as a reducing agent as described later) and the like. And an organic metal salt oxidizing agent or the like can be further contained as necessary. These components are often added to the same layer, but may be added separately to another layer if they can react.
For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later. However, by incorporating a reducing agent into the photosensitive material, an effect of promoting color image formation and the like can be obtained.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, a combination 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, or a combination of a red-sensitive layer, a first infrared layer, and a second infrared layer and so on. 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. The type of the dye-providing compound (yellow, magenta, cyan) to be combined with each of these photosensitive layers is optional when a color image is reproduced from image information converted into an electric signal, and a normal type color photosensitive material is used. There is no such restriction. The present invention can also be used for black-and-white light-sensitive materials or single-color light-sensitive materials.
The black-and-white light-sensitive material may be either a case where the dye-donating compound emits a black dye or a case where the dye-donating compound contains a mixture of yellow, magenta and cyan dye-donating compounds.

The photothermographic material includes a protective layer, an undercoat layer,
Various auxiliary layers such as an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer can be provided.

(Basic Structure and Preparation Method of Silver Halide Grains) Silver halides usable in the present invention include silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride, and chloroiodo. Any of silver bromide may be used, but preferred is silver iodobromide containing 30 mol% or less of silver iodide, silver chloride, silver bromide and silver chlorobromide.

The silver halide emulsion used in the present invention may be of a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, so-called multi-structure grains having different halogen compositions between the inside and the grain surface may be used. Of the multiple structure grains, those having a double structure may be particularly referred to as a core-shell emulsion. The silver halide used in the present invention is preferably a multi-structured grain, and a core-shell emulsion is more preferred. However, the present invention is not limited to this.

The silver halide emulsion used in the present invention is preferably a monodisperse emulsion.
The coefficient of variation described in the above item is preferably 20% or less.
More preferably 16% or less, still more preferably 10%
It is as follows. However, the present invention is not limited to this monodispersed emulsion. The average grain size of the silver halide grains used in the present invention is from 0.1 μm to 2.2 μm, preferably from 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be cubic, octahedral, high aspect ratio tabular, potato-shaped, or any other. More preferably, they are cubic emulsions. Specifically, U.S. Pat.
No. 500062, column 50, No. 4628021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17
029 (1978), JP-A-62-253159, etc. can be used.

In the process of preparing the silver halide emulsion of the present invention, when a so-called desalting step for removing excess salt is carried out, as a means for this purpose, gelling of gelatin, which has been known for a long time, is carried out by Nudel water washing. Method, and inorganic salts comprising polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, aliphatic acylated gelatin, aromatic A sedimentation method (flocculation) using acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Preferably, a sedimentation method using a compound represented by a sedimentation agent (a) or a sedimentation agent (b) described below is used, but the present invention is not limited thereto. An ultrafiltration method may be used without using any of the above settling agents. The removal of the excess salt may be omitted.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and chromium for various purposes. These compounds may be used alone,
Also, two or more kinds may be used in combination. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. Further, when it is contained, it may be uniformly contained in the particles, or may be localized on the surface or inside of the particles.

Preferred addition of iridium used in the present invention
The amount is 10 per mole of silver halide.^-9-10^-FourIn mole
Yes, more preferably 10^-8-10^-6Is a mole. core
In the case of shell emulsion, the core and / or shell
Indium may be added. As the compound, K_TwoIrC
l₆And K_ThreeIrCl₆Is preferably used. In addition,
The preferred amount of rhodium used in the light is silver halide.
10 per mole^-9-10^-6Is a mole. In addition, the present invention
The preferred addition amount of iron used in the above is 1 mole of silver halide.
10 ^-7-10^-3Mole, more preferably 10^-6
-10^-3Is a mole.

Some or all of these heavy metals are doped in advance in a fine grain emulsion such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide and the like, followed by adding this fine grain emulsion to obtain a halide. A method of locally doping the silver emulsion surface is also preferably used.

In the step of forming silver halide grains, rhodan salts, NH ₃ and tetra-substituted thioether compounds, organic thioether derivatives described in JP-B-47-11386, and JP-A-53-144319 are used as silver halide solvents.
And the like. In the stage of forming silver halide grains,
6-7781, JP-A-60-222842 and 60
Nitrogen-containing compounds such as those described in JP-A-122935 can be added.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloids, but hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates; sodium alginate, starch derivatives; polvinyl alcohol, polvinyl alcohol partial acetal , Poly-N-vinylpyrrolidone, polyacrylic acid,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin and Britain Society of
The Scientific Photography of Japan (Bull. Soc. Sci. Phot., Japan), No. 16, Page
Enzyme-treated gelatin as described in No. 30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

For other conditions, refer to Graph Graph
(P. Glafkides), "Chimie et Physique Photographique"
[Paul Montel, 1967], GFDuffin, Photographic Emulsion Chemistry (PhotographicEmu
lsion Chemistry)] [The Focal Press
cal Press), 1966], VL Zelikman et al., Making and Coating Photographic Emulsion
(Making and Coating Photographic Emulsion)
(The Focal Press, published in 1964)
Etc. may be referred to. 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 with a soluble halogen salt may be any of a one-side mixing method, a double-mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.

In order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (Japanese Patent Application Laid-Open Nos. 55-142329 and 55-158124; U.S. Pat. No. 3650575). During or after grain formation, the surface of the silver halide grain may be replaced with a halogen that forms a sparingly soluble silver halide grain. Further, the stirring method of 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. The preferred pH range is 2.2-6.0, more preferably 3.0.
５5.5.

The emulsion for the blue-sensitive layer used in the present invention comprises silver halide grains having a layer having a high silver iodide content on the grain surface described in Japanese Patent Application No. 3-308225. Silver halide emulsions which have been subjected to chemical sensitization before desalting and iodine ion addition are particularly preferred.

(Method of Adding Sensitizing Dye) The timing of adding the sensitizing dye may be basically any time. That is, at the beginning of the formation of silver halide emulsion grains (may be added before nucleation),
During or after formation, or at the beginning, during or after the desalting step, at the time of redispersion of gelatin, and before, during, during or after preparation of chemical sensitization, or during preparation of a coating solution. Preferably, it is added during or after the formation of silver halide grains, or before, during or after chemical sensitization. Addition after chemical sensitization means adding a sensitizing dye after all chemicals necessary for chemical sensitization have been added. US Patent 418375
As described in US Pat. No. 6,425,666, it may be present in a reaction system between a soluble silver salt (for example, silver nitrate) and a halide (for example, potassium bromide) before silver halide grains are formed. As described in (1), after the nucleation of silver halide grains and before the end of the step of forming silver halide grains, they may be present in the above reaction system. A sensitizing dye may be present in the reaction solution simultaneously with the formation of the silver halide grains, that is, simultaneously with the mixing of the silver salt and the halide. It is more excellent in storability under high temperature conditions and in gradation.

The concentration of the sensitizing dye-added solution, the solvent, the time of addition (the addition may be carried out all at once or over time), the temperature and the pH may be any conditions. Either addition at the liquid surface or addition in the liquid may be used. These conditions are described in detail in JP-A-3-110555 and the like.

(Types of Sensitizing Dyes) The sensitizing dyes used in the emulsion used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and the like. Hemioxonol dyes are included. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-18
No. 0550, No. 60-140335, RD17029
(1978), pages 12 to 13, and the like. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in JP-A-63-23145).

In the present invention, in any of the above addition methods, the total amount of the sensitizing dye may be added at one time.
Further, it may be added in several portions. Further, the sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or a halide.

The sensitizing dye is dissolved in a water-compatible organic solvent such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide, or acetone, or water (which may be alkaline or acidic) and added. Or two or more of the above may be used in combination. It may also be added in the form of a dispersion in a water / gelatin dispersion or in the form of a lyophilized powder. Further, it may be added in the form of a powder or a solution dispersed using a surfactant.

The sensitizing dye used in the emulsion of the present invention is described, for example, in JP-A-3-296745 and JP-A-4-31854.
Nos. 4,146,431 and 5-45828, and the like.

The use amount of the sensitizing dye is suitably from 0.000002 g to 20 g, preferably from 0.01 g to 2 g, per 100 g of silver used in the production of the emulsion.

In the present invention, the following compounds can be contained. This compound is often used for supersensitization, improvement of storage stability, and suppression of sensitivity change of a coating solution over time. The light-sensitive material of the present invention has more effective effects.

[0063]

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In the above formula, A represents a divalent aromatic residue. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an alkylthio group, an arylthio group, an amino group, Represents an unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, a heterocyclylamino group, an aryl group, a heterocyclyloxy group, or a mercapto group. However, at least one of A, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ has a sulfo group. W ₁ and W ₂ are each -CH =
Or -N =. However, either one of at least W ₁ and W ₂ represent -N =.

The above compounds are known compounds as supersensitizers of sensitizing dyes in general photographic materials for wet development processing (US Pat. Nos. 2,875,058 and 3,695).
888, JP-A-59-192242 and JP-A-59-192242.
This compound is also known as a supersensitizer in heat-developable color light-sensitive materials (see Japanese Patent Application Laid-Open No.
9-180550). Details and specific examples of the above compounds are described in JP-A-63-23145.

(Chemical Sensitization) The silver halide emulsion used in the present invention can be used as it is without chemical sensitization. However, it is preferable to use a chemical sensitized emulsion whose sensitivity has been increased. The chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or a combination thereof. In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium or tellurium, or chemical sensitization with a noble metal such as palladium or iridium may be combined with the above-described chemical sensitization.

Further, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound represented by (1,3,3a, 7) -tetraazaindene is also preferably used. The preferred range of the addition amount is 10 ^-1 to 10 ^-5 mol per mol of silver halide (Japanese Patent Application Laid-Open No. 62-1987)
253159).

The pH at the time of chemical sensitization is preferably from 5.3 to
10.5, more preferably 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur which can react with active gelatin or silver. Examples thereof include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid. ,
Rhodan, mercapto compounds and the like are used. In addition, U.S. Pat. Nos. 1,574,944 and 2,410,689.
No. 2,278,947, No. 2,728,668, and No. 3,656,955 can also be used.

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

In the present invention, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. In addition, JP
Silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-113235;
The acetylene silver described in 1-249944 is also useful.
Two or more organic silver salts may be used in combination. The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol. , Polyvinylpyrrolidone, acrylamide polymers, and other synthetic high molecular compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds.

In the case where a system for performing thermal development by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to rapidly absorb water. When the superabsorbent polymer is used for the dye-fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less, more preferably 10 g or less, and even more preferably 7 g or less per 1 m ² .

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

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.

Examples of the reducing agent used in the present invention include:
U.S. Pat. Nos. 4,500,626, columns 49-50, 4,483,914, columns 30-31, 4,33.
0,617, 4,590,152, JP-A-60-1985.
140335, pages (17) to (18), 57-4
No. 0245, No. 56-138736, No. 59-178
No. 458, No. 59-53831, No. 59-18244
No. 9, No. 59-182450, No. 60-119555
Nos. 60-128436 to 60-128439
No. 60-198540, 60-18174
No. 2, 61-259253, 62-244444
No. 62-131256 to No. 62-131256
No. 78-9 of EP 220,746 A2.
There are reducing agents and reducing agent precursors described on page 6 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 transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

As the diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent, any one which does not substantially move in the layer of the photosensitive material among the above-mentioned reducing agents may be used.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
Compounds described as electron donors in No. 0827 and dye-donating compounds having a diffusion-resistant and reducing property described later are exemplified. In the present invention, the addition amount of the reducing agent is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per mol of silver.

In the present invention, when silver ions are reduced to silver under high-temperature conditions, a compound which generates or releases a mobile dye in response to this reaction or vice versa, that is, a dye donor An active compound.

Examples of the dye-donating compound that can be used in the present invention include compounds (couplers) that form a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers include TH Ja
"The Theory of the Photographic Process" by mes # 4
Versions 291 to 334 and 354 to 361, JP-A-5
8-123533, 58-149046, 58
Nos. 149047, 59-111148 and 59-
No. 124399, No. 59-174835, No. 59-2
No. 31539, No. 59-231540, No. 60-29
No. 50, No. 60-2951, No. 60-14242,
Nos. 60-23474 and 60-66249.

As another example of the dye donating compound,
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI]. (Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like latent image. (Dye-Y) _n -Z corresponding to the photosensitive silver salt having the formula (Dye-Y) _n -Z, or Dye is released, and the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusivity between _{n and} Z,
Represents 1 or 2, and when n is 2, two Dye-Y
May be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. In the following,-is to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "is" to form a diffusible dye image (positive dye image) in response to the development of silver halide. (A negative dye image).

Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and the like. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

US Pat. No. 4,559,290, EP 220,746 A2, US Pat. No. 4,783,
No. 396, JP-A-87-6199, and the like, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples include U.S. Pat. No. 4,139,389.
No. 4,139,379, JP-A-59-18533.
Nos. 3,232,107, and JP-A-59-84453, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction. No. 101649, No. 61-88257, RD
24025 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-5
No. 6,142,530, U.S. Pat. No. 4,343,893.
Nos. 4,619,884, etc., which release a diffusible dye by cleavage of a single bond after reduction;
A nitro compound releasing a diffusible dye after electron acceptance described in U.S. Pat. No. 4,450,223 and the like, and a diffusible dye releasing after electron acceptance described in U.S. Pat. No. 4,609,610 and the like And the like.

[0086] More preferred are EP 220,746 A2, published technical report 87-6199, U.S. Pat. No. 4,783,396, and JP-A-63-2016.
No. 53, 63-201654 and the like, compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268
No. 42, a compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group in one molecule.
No. 71344 describes that a PO-X bond (X
Has the same meaning as described above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Compounds having a bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group are exemplified. Further, compounds described in JP-A-1-161237 and JP-A-1-161342, in which a single bond is cleaved after reduction by a π bond conjugated to an electron-accepting group to release a diffusible dye, can also be used. Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Examples are EP 220,746 A2 or US Pat. No. 4,783,39.
Compounds (1) to (3) and (7) to (1) described in No. 6
0), (12), (13), (15), (23)-(26), (3
1), (32), (35), (36), (40), (41), (4
4), (53)-(59), (64), (70), Published Technical Report 87
Compounds (11) to (23) described in US Pat.

Compounds which have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940 and 4,474,867
No. 4,483,914 and the like.

Compounds that are reducible to silver halide or organic silver salts and release diffusible dyes when the partner is reduced (DRR compounds). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312 and 4,053,312,
Nos. 4,055,428 and 4,336,322, JP-A-59-65839, JP-A-59-69839, and JP-A-5-6939
No. 3-3819, No. 51-104343, RD174
No. 65, U.S. Pat. Nos. 3,725,062 and 3,72
Nos. 8,113 and 3,443,939;
Nos. 116537, 57-179840 and U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the aforementioned US Pat. No. 4,500,62.
The compounds described in Columns 22 to 44 of No. 6 can be mentioned, and among them, the compound (1) described in the above-mentioned U.S. Pat.
~ (3), (10) ~ (13), (16) ~ (19), (28) ~
(30), (33)-(35), (38)-(40), (42)-
(64) is preferred. U.S. Pat. No. 4,639,408
No. 37-39 are also useful.

In addition, as the above-mentioned couplers and dye-donating compounds other than the general formula [LI], dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58) Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
5,957, Research Disclosure Magazine, 19
April, 76, pp. 30-32), leuco dyes (U.S. Pat. Nos. 3,985,565, 4,022,617, etc.) and the like can also be used.

The hydrophobic additives such as a dye-donating compound and a diffusion-resistant reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-Open No. 59-83154
Nos. 59-178451 and 59-178452
Nos. 59-178453 and 59-178454
And high-boiling organic solvents described in JP-A-59-178455, JP-A-59-178457, and the like, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donating compound used.
It is as follows. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-39853
A dispersion method using a polymer described in No. 59943 can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, those described as surfactants on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the present invention, a non-diffusible filter dye can be contained for the purpose of improving sharpness and the like. If necessary, a filter dye having absorption in the infrared region can be used. For details of such filter dyes, see JP-A-4-31854 and JP-A-4-217243.
Nos. 4-276744 and 5-45834.

In a system for forming an image by diffusion transfer of a dye, a dye-solid material is used together with a photosensitive 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. As for the relationship between the photosensitive 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 US Pat. No. 4,500,626.
No. 58-59 and JP-A-61-88256 (32)
-Mordants described in (41), JP-A-62-244043
And Nos. 62-244036. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

The dye-fixing material may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing material, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing material. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 62-245253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X).
-22-3710) are effective. In addition, JP
Silicone oils described in JP-A-2155953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (US Pat. No. 3,352,6)
No. 81), benzophenone-based compounds (JP-A-46-
2784, etc.), and JP-A-54-48535,
There are compounds described in JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of the metal complex include U.S. Patent Nos. 4,241,155 and 4,24.
Nos. 5,018, columns 3 to 36; 4,254,195, columns 3 to 8; JP-A Nos. 62-174741 and 61-88.
Nos. 256 (27) to (29), 63-199248,
There are compounds described in JP-A-1-75568 and JP-A-1-74272. Examples of useful anti-fading agents are described in JP-A-62-215272, pages (125) to (137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or supplied to the dye-fixing material from outside such as a photosensitive material. You may. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used for the light-sensitive material and 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 photosensitive material. For example, K. Veenkataraman ed., “The Chemis
try of Synthetic Dyes, Vol. 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 an anti-fading agent.

Examples of the hardener used in the constituent layers of the light-sensitive material and the dye-fixing material include US Pat. No. 4,678,739 No. 4
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing material, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457. The constituent layers of the photosensitive material and the dye fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

A matting agent can be used for the photosensitive material and the dye fixing material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness, and preventing Newton's ring, but also for the purpose of making the dye fixing material surface (image surface) non-glossy.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used for the light-sensitive material and / or the 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 From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. A specific example is disclosed in U.S. Pat.
493 and JP-A-62-65038. In a system in which thermal development and transfer of a dye are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing material from the viewpoint of improving the storage stability of the photosensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a combination of a compound (hereinafter referred to as a complex-forming compound) capable of forming a complex with a metal ion constituting the hardly-soluble metal compound, Compounds that generate a base by electrolysis described in JP-A-61-232451 can also be used as the base precursor. In particular, the former method is effective. This poorly soluble metal compound and complex forming compound
It is advantageous to separately add the light-sensitive material and the dye-fixing material.

In the present invention, various development stopping agents can be used in the light-sensitive material and / or the dye-fixing material for the purpose of always obtaining a constant image with respect to fluctuations 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 further details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, as a support for the light-sensitive material or the dye-fixing material, a support that can withstand the processing temperature is used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used.

These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

As a method of exposing and recording an image on a photosensitive material, image information is transmitted through an electric signal to a light emitting diode,
There are a method of performing exposure by emitting various lasers and the like, and a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system. Specifically, JP-A-2-129625, Japanese Patent Application Nos. 3-338182, 4-009388, and 4-
The exposure method described in JP-A-281442 can be used.

As a light source for recording an image on a photosensitive material,
As mentioned above, light emitting diode, laser light source, CRT
Light sources such as those described in U.S. Pat. No. 4,500,626, column 56, such as light sources, can be used.

[0114]

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

Example 1 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Sensitive Layer)] In a well-stirred aqueous solution having the composition shown in Table 1, the solution (I) having the composition shown in Table 2 and ( Solution II) was added simultaneously over 13 minutes, and 10 minutes later, solution (III) and solution (IV) having the composition shown in Table 2 were added over 33 minutes.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

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Further, from 13 minutes after the start of the addition of the solution (III), 27
Over a period of minutes, 150 cc of a 0.35% aqueous solution of a sensitizing dye was added.

[0121]

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After washing with water and desalting (using a precipitant (a) at a pH of 4.1) according to a conventional method, 22 g of lime-treated ossein gelatin was added, and the pH and pAg were adjusted to 6.0 and 7.0, respectively. After adjusting to 9, it was chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 3. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0123]

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[0124]

[Table 3]

[0125]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Sensitive Layer)] A solution (I) having a composition shown in Table 5 was added to a well-stirred aqueous solution having a composition shown in Table 4. Solution II) was added simultaneously over 18 minutes, and 10 minutes later, solution (III) and solution (IV) having the composition shown in Table 5 were added over 24 minutes.

[0127]

[Table 4]

[0128]

[Table 5]

Lime-treated ossein gelatin (calcium content: 150 p) after washing with water and desalting (using a sedimenting agent (b) at a pH of 3.9) and decalcifying in a conventional manner.
pm or less), redispersion at 40 ° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, pH 5.9, pAg 7 Adjusted to .8. Then, using the chemicals shown in Table 6, 7
Chemical sensitization at 0 ° C. At the end of the chemical sensitization, a sensitizing dye was added as a methanol solution (solution having the composition shown in Table 7). Furthermore, after chemical sensitization, the temperature was lowered to 40 ° C.
200 g of a gelatin dispersion of a stabilizer described later was added, and the mixture was stirred well and stored. The yield of the obtained emulsion was 9
A monodisperse cubic silver chlorobromide emulsion of 38 g with a coefficient of variation of 12.6% had an average grain size of 0.25 μm.

[0130]

[Table 6]

[0131]

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[0132]

[Table 7]

[0133]

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Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Sensitive Layer)] A solution (I) having a composition shown in Table 9 was added to a well-stirred aqueous solution having a composition shown in Table 8. Solution II) was added simultaneously over 18 minutes, and 10 minutes later, solution (III) and solution (IV) having the composition shown in Table 9 were added over 24 minutes.

[0135]

[Table 8]

[0136]

[Table 9]

After washing with water and desalting (using a precipitant (a) at a pH of 3.8) according to a conventional method, 22 g of lime-treated ossein gelatin was added, the pH was 7.4, and the pAg was 7. After the adjustment to 8, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are as shown in Table 10. The yield of the obtained emulsion was 680 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0138]

[Table 10]

A method for preparing a gelatin dispersion of colloidal silver will be described.

To the well-stirred aqueous solution having the composition shown in Table 11, a solution having the composition shown in Table 12 was added over 24 minutes. Then, after washing with water using the sedimentation agent (a), 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 51
2 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0141]

[Table 11]

[0142]

[Table 12]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Gelatin dispersions of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound were each prepared as shown in Table 13. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution. An aqueous phase component heated to about 60 ° C. was added to this solution, followed by stirring and mixing, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion. Further, a gelatin dispersion of a cyan dye-donating compound was added to an ultra-loca module (Asahi Kasei ultra-loca module: A
Using CV-3050), dilution and concentration with water were repeated to reduce the amount of ethyl acetate to 17.6 of the amount of ethyl acetate in Table 13.

[0145]

[Table 13]

A gelatin dispersion of the reducing agent was prepared according to the recipe in Table 14. That is, each oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to this solution, and the mixture is stirred and mixed.
Dispersed at 000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion by using a vacuum organic solvent removal apparatus.

[0147]

[Table 14]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 15. That is, each oil phase component is dissolved at room temperature,
The aqueous phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed. Then, the mixture was homogenized for 10 minutes at 10,000 rpm.
m. Water was added thereto and stirred to obtain a uniform dispersion.

[0149]

[Table 15]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 16. That is, after mixing and dissolving each component, the mixture is mixed with glass beads having an average particle size of 0.75 mm using a mill.
Dispersed for minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.1.
The thing of 02 μm was used. )

[0151]

[Table 16]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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Using the above, a photothermographic material 100 shown in Table A was prepared.

[0166]

[Table 17]

[0167]

[Table 18]

[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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The light-sensitive materials 101 to 106 were prepared in the same manner as the light-sensitive material 100, except that the comparative compounds shown in Table 19 or the compounds of the present invention were used in the seventh layer of the light-sensitive material 100 in the amounts shown in Table 19. Created.

[0174]

[Table 19]

[0175]

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Next, a method for preparing the dye-fixing material will be described.

A dye-fixing material 200 having the composition shown in Table 20 was prepared. The structure of the surface layer (1) is as shown in Table 21, and the structure of the back layer (1) is as shown in Table 22. The structure of the support (1) is as shown in Table 23, and the physical properties are as shown in Table 24.

[0178]

[Table 20]

[0179]

[Table 21]

[0180]

[Table 22]

[0181]

[Table 23]

[0182]

[Table 24]

The compounds in Tables 21 and 22 are as follows.

Water-soluble polymer (11) Sumikagel L5-H (manufactured by Sumitomo Chemical Co., Ltd.) Water-soluble polymer (12) Copper carrageenan (manufactured by Taito Corporation) Water-soluble polymer (13) Dextran (molecular weight 70,000)

[0185]

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[0186]

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Fluorescent whitening agent (11) 2,5-bis (5-t-benzoxazolyl (2)) thiophene High-boiling organic solvent (11) Empara 40 (manufactured by Ajinomoto Co.) Matting agent (11) Benzoguanamine resin (average particle size 15 μm) Latex (11) Nipol LX-814 manufactured by Zeon Corporation

[0188]

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The dye-fixing material 201 was prepared in the same manner as the dye-fixing material 200, except that the comparative compound shown in Table 25 or the compound of the present invention was used in the fourth layer of the dye-fixing material 200 in the amount shown in Table 25. ~ 205 were created.

[0190]

[Table 25]

[0191]

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These photosensitive materials were exposed under the exposure conditions shown in Table 26 using an exposure apparatus having an optical system as shown in FIG. 2 of Japanese Patent Application No. 4-281442.
/ M ² of water was applied and superimposed such that the dye-fixing material and the membrane surface were in contact. The combination of photosensitive material and dye fixing material
It is as shown in Table 27. After heating for 35 seconds using a heat drum adjusted so that the temperature of the film that absorbed water was 83 ° C., the dye fixing material was separated from the photosensitive material, and cyan, yellow, and magenta images were obtained on the dye fixing material. The highest and lowest concentrations were measured under X-RITE status A conditions. Stain was evaluated by the difference between the minimum density of yellow after image output and the minimum density of yellow after 3 days at 80 ° C. and 90% RH. Table 28 summarizes the above results. The minimum density after image output is the comparative example,
There was no significant difference in the present invention.

[0193]

[Table 26]

[0194]

[Table 27]

[0195]

[Table 28]

As can be seen from Table 28, by using the light-sensitive material and the dye-fixing material using the compound of the present invention,
Compared with the comparative example, it can be seen that the stain at the time of storing the image is improved and the image density is not reduced.

[0197]

By using the compound represented by the general formula (1) of the present invention in a photothermographic material and / or a dye-fixing material, it is possible to reduce the occurrence of stain during image storage without lowering the image density. It can be effectively prevented.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 8/40 505 G03C 8/40 504 G03C 8/26 G03C 8/56

Claims (2)

(57) [Claims] 1. A photothermographic material having at least a photosensitive silver halide emulsion, a binder and a dye-providing compound on a support, comprising at least one compound represented by the following general formula (1). Characteristic photothermographic material. Embedded image In the general formula (1), each independently R ₁ and R ₂ represents an aromatic hydrocarbon group or a heterocyclic group, R _3, R ₄ and R ₅
Each independently represents a hydrogen atom or a lower alkyl group.
m _{1 to} m ₆ each independently represent an integer of 1 . n is 0 or 1
K and j each represent an integer of 0 to 4, k + j is 1 or more, and n + k + j is an integer of 1 to 4. A represents an n + k + j-valent group, and when n + k + j = 2, A may be a single bond. 2. A dye-fixing material having at least a binder and a mordant on a support, wherein the dye-fixing material contains at least one compound represented by the following general formula (1). Embedded image In the general formula (1), each independently R ₁ and R ₂ represents an aromatic hydrocarbon group or a heterocyclic group, R _3, R ₄ and R ₅
Each independently represents a hydrogen atom or a lower alkyl group.
m _{1 to} m ₆ each independently represent an integer of 1 . n is 0 or 1
K and j each represent an integer of 0 to 4, k + j is 1 or more, and n + k + j is an integer of 1 to 4. A represents an n + k + j-valent group, and when n + k + j = 2, A may be a single bond.