JPH07191444A - Heat developable color image forming material - Google Patents

Abstract

PURPOSE:To prevent fog and decrease in sensitivity during storage of the raw material is stored and to obtain high sensitivity by incorporating substantially no org. silver salt into a layer containing photosensitive silver halide and incorporating an org. silver salt into at least one layer containing no photosensitive silver halide. CONSTITUTION:This heat developable color photosensitive material has at least photosensitive silver halide, dye-donating material and binder on a paper base. The layer containing photosensitive silver halide does not substantially contain org. silver salt, but a layer containing no photosensitive silver halide contains org. silver salt A preferable example of the org. silver salt is obtd. by the reaction of at least one kind of compd. expressed by the formula with a supplier of silver ion such as silver nitrate. In formula, Z1, Z2, Z3 are groups of atoms to form 5-to 9-member heterorings. The layer substantially contains no org. silver salt means that the total amt. of org. silver salt in one layer containing silver halide is <0.01mol calculated as silver to one mol of silver halide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a high-sensitivity heat-developable color light-sensitive material having low fog and good raw storability.

[0002]

Photothermographic materials are known in the art. For example, a method of forming a dye image by a coupling reaction between an oxidant of a developing agent and a coupler is described in U.S. Pat. Nos. 3,761,270 and 4,021,240. Have been described. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Further, recently, a method has been proposed in which a diffusible dye is released or formed imagewise by heat development and the diffusible dye is transferred 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, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
18443, 61-238056, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by being oxidized and reduced by the reducing agent remaining without being oxidized. In addition, U.S. Pat. No. 4,783,396 and Kokai Giho 87-6199 (Vol. 12, No. 22) disclose that N-X bond (X is an oxygen atom, a nitrogen atom or a Photothermographic color light-sensitive materials using compounds which release diffusible dyes by reductive cleavage of (representing sulfur atoms) are described.

Further, as described in "Image Information" October issue (published on October 1, 1993) issued by Ken Kokumai Ken Kogyo Kogyo Kaisha, Ltd., progress in computer graphics has been remarkable in recent years. In addition, various high-quality color printers (color hard copy) for outputting these image information have been developed. Among them, a printer using a heat-developable color light-sensitive material using silver halide, such as Fujis Pictographography 3000 manufactured by Fuji Photo Film Co., Ltd., is on sale. It is a method of exposure using three laser diodes (LD), and the spectral sensitivity of the photosensitive material is also spectrally sensitized in the infrared light region according to the emission wavelength of the LD.

By the way, it is known that fog (heat fog) unexpectedly occurs in normal wet development particularly in the development of a photothermographic material. In order to prevent this, various organic compounds called antifoggants are used, but these have the effect of reducing the sensitivity. Further, as described in JP-A-4-243256, a light-sensitive material using a paper support has a lower cost than using a polymer film (such as polyethylene terephthalate), and the light-sensitive material can be easily discarded. Although it has the advantage that it is present, it has the drawback that thermal fog is likely to occur. In order to improve this, it is necessary to use a large amount of antifoggant, and thus it is difficult to increase the sensitivity.

In general, in the spectral sensitization in the infrared region, there is a problem that the sensitivity is apt to decrease with the lapse of time before use, and various stabilizers are used to solve this problem. However, even though these stabilizers can prevent the sensitivity from decreasing with time, they have the problem of decreasing the absolute sensitivity before the time, which hinders the sensitization of a light-sensitive material spectrally sensitized to infrared rays. Was there. Therefore, it has been difficult to further increase the sensitivity of the photothermographic material that has been spectrally sensitized to infrared rays. Furthermore, among the photothermographic materials spectrally sensitized to infrared rays,
In a light-sensitive material containing a filter dye that is non-diffusive and has an absorption maximum in the infrared region, which is often used to improve color turbidity due to overlapping spectral sensitivities, the filter dye reduces the sensitivity of the silver halide emulsion during raw storage. Since it may occur, it is necessary to use a large amount of stabilizer.

On the other hand, it is known to use an organic silver salt such as silver benzotriazole in a photothermographic material. For example, JP-B-5-54107 shows that a high maximum concentration can be obtained by using 0.01 to 1.0 mol of an organic silver salt (organic silver salt oxidizing agent) per mol of silver halide. ing. However, Tokuhei 5-5
The invention described in No. 4107 is to use an organic silver salt in the same layer as a silver halide emulsion in a method of forming an image in a substantially water-free state. Also,
In the above-mentioned JP-A-4-243256, in the image forming method using a small amount of water as in the present invention, the amount of the organic silver salt used in the heat-developable photosensitive material using a paper support is changed to the total amount of silver halide. It is described that when the content is less than 1 mol%, fog, graininess, and raw storability are improved. However, the invention of JP-A-4-243256 also describes the effect of containing an organic silver salt in the same layer as silver halide. Furthermore, JP-A-1-100
No. 177, in the description of the invention of the method for producing an organic silver salt, it is described that the layer to which the organic silver salt is added may be the same layer as the silver halide or an adjacent layer. It has not been shown to be particularly effective when used. Further, Japanese Patent Publication No. 48900/1993 describes that an organic silver salt is contained in an intermediate layer in order to prevent color turbidity, but thermal development containing an organic silver salt in the same layer as silver halide. It is an invention in image formation limited to color light-sensitive materials.

Therefore, in a heat-developable color light-sensitive material which uses a paper support and does not contain an organic silver salt in the silver halide-containing layer, the layer containing no silver halide contains an organic silver salt. It has the effect of preventing fog during storage and the sensitivity reduction, and it is possible to reduce the amount of antifoggants and stabilizers used, and it is not expected that the sensitivity will eventually improve. Was that.
Further, it is well known that the technique of sensitizing a silver halide emulsion not only raises the absolute sensitivity of the light-sensitive material but also leads to other performance improvement. For example, it is possible to improve the performance by reducing the grain size of the silver halide emulsion due to the high sensitivity and reducing the development temperature dependency at the same sensitivity.

[0010]

It is an object of the present invention to obtain a heat-developable color light-sensitive material having a high sensitivity by preventing fog and deterioration in sensitivity during raw storage in a heat-developable color light-sensitive material using a paper support.

[0011]

The above objects have been achieved by the present invention described below. That is, in a heat-developable color light-sensitive material having at least a light-sensitive silver halide, a dye-donor substance, and a binder on a paper support,
A heat-developable color light-sensitive material characterized in that a layer containing substantially no organic silver salt in a layer containing a photosensitive silver halide and containing an organic silver salt in a layer not containing a photosensitive silver halide is used. That is.

The present invention will be described in more detail below.

Organic compounds that can be used to form the above organic silver salt oxidizing agents include US Pat. No. 4,500,6.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination.

More preferable specific examples of the organic silver salt used in the present invention are shown in JP-A-1-100177. That is, it is a silver salt obtained by reacting at least one of the compounds represented by the following general formula (I), (II) or (III) with a silver ion donor such as silver nitrate.

[0015]

[Chemical 2]

[In the formula, Z ₁ , Z ₂ and Z ₃ each represent an atomic group necessary for forming a 5- to 9-membered heterocycle. Here, the hetero ring includes a ring in which a benzene ring or a naphthalene ring is condensed. The method described in JP-A-1-100-77 is preferably used as the method for producing the organic silver salt, but the present invention is not limited thereto.

The compound used for producing the organic silver salt in the present invention will be described in detail. In formula (I), Z ₁ represents an atomic group necessary for forming a 5-membered to 9-membered (especially 5-membered, 6-membered or 9-membered) heterocycle. The heterocyclic ring completed by Z ₁ in the general formula (I) is preferably a 5-membered, 6-membered or 9-membered heterocyclic ring containing at least one nitrogen atom, and particularly containing two or more nitrogen atoms, Or containing at least one nitrogen atom and an oxygen atom or a sulfur atom 5
A 6-, 9-, or 9-membered heterocycle is preferred. The term "heterocycle" as used herein also includes those condensed with a benzene nucleus or a naphthalene nucleus.

Examples of such compounds include benzotriazole, JP-A-58-118638 and JP-A-58-118.
Benzotriazoles and benzimidazoles described in 639 and the like, pyrazoloazoles described in JP-A-62-96940 {for example, 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5 -B] pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,
4] triazoles, 1H-pyrazolo [1,5-d] tetrazoles and 1H-pyrazolo [1,5-a] benzimidazoles}, triazoles, 1H-tetrazoles, carbazoles, saccharins, imidazoles, 6-aminopurines and the like.

Among the compounds of general formula (I), the compounds of general formula (I-1) are preferred.

[0020]

[Chemical 3]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkoxy group, an aryl group, a hydroxy group, a sulfo group or a salt thereof (eg sodium salt). Salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (for example, sodium salt, potassium salt, ammonium salt), —CN, —NO ₂ , —NRR ′, —COOR, —
_{CONRR ', - NHSO 2 R,} -SO 2 NRR', represent (representing where, R and R 'are each a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.)

Specific examples of the compound represented by the general formula (I) include the following compound examples. For example, benzotriazole, 4-hydroxybenzotriazole, 5-hydroxybenzotriazole, 4-sulfobenzotriazole, 5-sulfobenzotriazole, benzotriazole-4-sulfonic acid sodium salt,
Sodium benzotriazole-5-sulfonate, potassium benzotriazole-4-sulfonate, potassium benzotriazole-5-sulfonate, ammonium benzotriazole-4-sulfonate, ammonium benzotriazole-5-sulfonate, 4-carboxybenzotriazole , 5-carboxybenzotriazole, 4
-Sulfo-5-benzenesulfonamide benzotriazole, 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole, 4-sulfo-5-ethoxycarbonylmethoxybenzotriazole, 4-hydroxy-5
-Carboxybenzotriazole, 4-sulfo-5-carboxymethylbenzotriazole, 4-sulfo-5-
Ethoxycarbonylmethylbenzotriazole, 4-sulfo-5-phenylbenzotriazole, 4-sulfo-
5- (p-nitrophenyl) benzotriazole, 4-
Sulfo-5- (p-sulfophenyl) benzotriazole, 4-sulfo-5-methoxy-6-chlorobenzotriazole, 4-sulfo-5-chloro-6-carboxybenzotriazole, 4-carboxy-5-chlorobenzotriazole , 4-carboxy-5-methylbenzotriazole, 4-carboxy-5-nitrobenzotriazole, 4-carboxy-5-aminobenzotriazole, 4-carboxy-5-methoxybenzotriazole, 4-hydroxy-5-aminobenzotriazole ,
4-hydroxy-5-acetamidobenzotriazole, 4-hydroxy-5-benzenesulfonamide benzotriazole, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole, 4-hydroxy-
5-ethoxycarbonylmethoxybenzotriazole,
4-hydroxy-5-carboxymethylbenzotriazole, 4-hydroxy-5-ethoxycarbonylmethylbenzotriazole, 4-hydroxy-5-phenylbenzotriazole, 4-hydroxy-5- (p-nitrophenyl) benzotriazole, 4- Hydroxy-5
(P-Sulfophenyl) benzotriazole, 4-sulfo-5-chlorobenzotriazole, 4-sulfo-5-
Methylbenzotriazole, 4-sulfo-5-methoxybenzotriazole, 4-sulfo-5-cyanobenzotriazole, 4-sulfo-5-aminobenzotriazole, 4-sulfo-5-acetamidobenzotriazole, benzotriazole-4-carboxylic Sodium acid,
Sodium benzotriazole-5-carboxylate, potassium benzotriazole-4-carboxylate, potassium benzotriazole-5-carboxylate, ammonium benzotriazole-4-carboxylate, ammonium benzotriazole-5-carboxylate, 5-carbamoylbenzotriazole 4-sulfamoylbenzotriazole, 5-carboxy-6-hydroxybenzotriazole, 5-carboxy-7-sulfobenzotriazole,
4-hydroxy-5-sulfobenzotriazole, 4-
Hydroxy-7-sulfobenzotriazole, 5,6-
Dicarboxybenzotriazole, 4,6-dihydroxybenzotriazole, 4-hydroxy-5-chlorobenzotriazole, 4-hydroxy-5-methylbenzotriazole, 4-hydroxy-5-methoxybenzotriazole, 4-hydroxy-5-nitro Benzotriazole, 4-hydroxy-5-cyanobenzotriazole, 4-carboxy-5-acetamidobenzotriazole, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole, 4-carboxy-5-carboxymethylbenzotriazole, 4-carboxy- 5-phenylbenzotriazole, 4-carboxy-5- (p
-Nitrophenyl) benzotriazole, 4-carboxy-5-methyl-7-sulfobenzotriazole, imidazole, benzimidazole, pyrazole, urazole, 6-aminopurine,

[0023]

[Chemical 4]

And the like. You may use these 2 or more types together.

Next, the compound represented by the general formula (II) will be described. In formula (II), Z ₂ represents an atomic group necessary for forming a 5-membered to 9-membered (especially 5-membered, 6-membered or 9-membered) heterocycle. At least one ring is completed by Z _{2 in the} above general formula (including C and N in the formula)
5-membered, 6-membered or 9-membered heterocycles containing 1 nitrogen atom are preferred, especially 5 members containing 6 or more nitrogen atoms, or 5 or 6 members containing one or more nitrogen atoms and oxygen or sulfur atom.
A 9-membered or 9-membered heterocycle is preferred. Here, the heterocycle includes those condensed with a benzene nucleus or a naphthalene nucleus.

Examples of such compounds include 2-mercaptobenzothiazoles, 2-mercaptobenzimidazoles, 2-mercaptothiadiazoles and 5-mercaptotetrazoles.

The following compounds may be mentioned as specific examples of the compound represented by the general formula (II), but the present invention is not limited to the following examples.

[0028]

[Chemical 5]

Next, the compound represented by the general formula (III) shown in Chemical formula 2 will be explained. In formula (III), Z ₃ represents an atomic group necessary for forming a 5-membered to 9-membered (especially 5-membered, 6-membered or 9-membered) heterocycle. The ring completed by Z _{2 in the} above general formula is preferably a 5-membered, 6-membered or 9-membered heterocycle containing at least one nitrogen atom, particularly containing two or more nitrogen atoms, or 1 nitrogen atom.
A 5-membered, 6-membered, or 9-membered heterocycle containing one or more and an oxygen atom or a sulfur atom is preferable. Here, the heterocycle includes those condensed with a benzene nucleus or a naphthalene nucleus, or a nitrogen-containing heterocycle having various substituents.

Examples of such compounds include hydroxytetraazaindenes, hydroxypyrimidines, hydroxypyridazines, hydroxypyrazines and the like.

The following compounds may be mentioned as specific examples of the compound represented by the general formula (II), but the present invention is not limited to the following examples.

[0032]

[Chemical 6]

In the present invention, the above general formulas (I) and (II) are used.
Alternatively, the compound (III) is mixed with silver nitrate in a suitable reaction medium to form a silver salt of the compound (hereinafter referred to as an organic silver salt). It is also possible to replace part of the silver nitrate with another silver ion donor (eg, silver chloride, silver acetate).

The method of adding these reaction reagents is arbitrary.
The compounds of the general formulas (I) to (III) may be placed in a reaction vessel in advance, and silver nitrate may be added thereto, or conversely, silver nitrate may be placed in the reaction vessel, and then the compounds of the general formula (I) are added. The compounds (1) to (III) may be added. Moreover, after a part of the compounds of the general formulas (I) to (III) is placed in a reaction vessel and a part of silver nitrate is added, the rest of the general formulas (I) to
The compound (III) and silver nitrate may be added sequentially.
Further, silver nitrate and the compounds of the general formulas (I) to (III) can be added simultaneously to the reaction vessel. It is preferable to stir during the reaction.

The compounds of the general formulas (I) to (III) are usually mixed with silver nitrate in a ratio of 0.8 to 100 mol per mol of silver, but depending on the kind of the compound, the amount may be outside this range. It can also be used. The addition rate of silver nitrate or a compound may be adjusted so as to control the silver ion concentration during the reaction.

The above organic silver salt may be added to one layer containing no silver halide or may be added to a plurality of layers. The layer to be added is a layer containing no silver halide emulsion in the hydrophilic colloid layer provided on the side having a silver halide emulsion layer such as a protective layer, an intermediate layer, a so-called undercoat layer between the support and the emulsion layer. Any layer will do as long as it is present. Also,
The total coating amount of the organic silver salt is suitably 0.01 mg / m ² to 10 g / m ² in terms of silver.

In the present invention, the phrase "substantially free of an organic silver salt in a layer containing a photosensitive silver halide" means that the total content of the organic silver salt contained in the same layer as the silver halide is the silver halide. It means less than 0.01 mol in terms of silver with respect to 1 mol.

Next, the paper support used in the present invention will be described. The paper support used in the present invention basically includes all supports containing paper.

The support used in the light-sensitive material of the present invention is preferably one that can withstand the processing temperature,
In general, paper or a mixed paper of synthetic resin pulp such as polyethylene and natural pulp can be used.

The paper used as the support may be any paper such as photographic base paper, plain paper, fine paper, Yankee paper and the like. A particularly preferred support has improved smoothness.

The support preferably used in the present invention is, for example, coated paper. Coated paper is a mixture of mineral pigments such as clay and an adhesive (eg casein, starch, latex, polyvinyl alcohol or a combination thereof) on one or both sides of a base paper (eg fine paper, medium paper, etc.). It refers to a paper that was applied, depending on the paint coating amount, art paper (coated amount 1m ² per 20g before and after), coated paper (coated amount 1m ² per 10g front and rear), lightweight coated paper (coated amount 1m ² per 5g (Before and after), and after the paint has been applied, while it still retains its plasticity, it is pressed into a mirror-finished dryer and dried to include cast-coated paper that does not have strong gloss. "Pulp and Paper Technical Handbook"
1982, pp. 415, 535-536, etc.).

Since this coated paper has a high surface smoothness even when the base paper has a small thickness (in particular, the surface smoothness of the CASCOAT paper is extremely high), the surface of the coating film of the photosensitive layer coated thereon is also smooth. become. Therefore, the adhesiveness when the light-sensitive material and the dye-fixing material are superposed on each other becomes very high, and it is easy to prevent uneven density.

[0043] The thickness of Coated papers for use in the present invention, weighed ^{20g / m 2 ~200g / m 2} , in particular a relatively thin ^{50g / m 2 ~100g / m 2} ( light) is preferred.

The above supports can be used alone or as a support laminated on one side or both sides with a synthetic polymer such as polyethylene. At this time, polyethylene used is effective from low density to high density.

Further, an electron beam curable resin composition containing a pigment may be applied and cured to be used as a support. These methods are particularly effective for paper, mixed paper, or coated paper in order to improve smoothness.

In the present invention, in order to impart antistatic properties and / or slip properties, it is also possible to use a support whose surface is coated with a conductive metal oxide such as alumina sol or SnO ₂ or TiO ₂ .

The surface state of the support may be glossy or matte. The back side may be glossy or matte. Preferably, the back layer side is a matte surface to prevent adhesion.

It is also possible to use a support whose surface is treated by vapor deposition with a metal such as aluminum.

In the present invention, a coated paper coated on both sides with a paper support is used for the purpose of improving the curl balance of the light-sensitive material. Specifically, double-sided coated paper,
It is effective to use a one-side coated / one-side cast paper or a two-side cast paper support.

Further, with a polymer such as polyethylene,
It is preferable to use a paper support laminated on both sides,
Further, it may be effective to use polyethylene having different polyethylene densities on both sides.

Further, it is effective to use a back layer. In this case, the back layer should contain colloidal silica, superabsorbent polymer, polymer latex, surfactant, nonionic polymer (polyvinylpyrrolidone, dextran, etc.). Is especially effective.

As described above, the curl can be adjusted by the support or the back layer. However, when a heat-developable image forming apparatus equipped with a roller for carrying is used, the curl can be adjusted vertically with respect to the carrying plane of the photosensitive material. It is preferable that the amount of curl in the vertical direction is equal to or smaller than the diameter of the conveying roller that abuts in the temperature rising state.

The back layer is formed by coating a hydrophilic colloid layer on a support opposite to the emulsion layer and drying. Examples of the hydrophilic colloid substance include those mentioned above. The back layer may be one layer, or two or more layers. The thickness of the back layer is not limited,
The thickness is preferably 0.5 to 15 μm, particularly 1 to 10 μm. No particular limitation on the amount of binder in the back layer, but it is appropriate range of normal ^{0.5g / m 2 ~15g / m 2} .

In the present invention, a non-diffusible filter dye may be contained for the purpose of improving sharpness and color separation. If necessary, a filter dye having absorption in the infrared region can be used.

The details of the non-diffusible filter dye having a maximum absorption at a wavelength of 700 nm or more which is preferably used in the present invention are described in JP-A-4-31854 and 4-2.
No. 17243, No. 4-276744, No. 5-4583.
No. 4 etc. Among them, the filter dye particularly preferably used is the filter dye represented by the general formula (S).

[0056]

[Chemical 7]

Here, R ₁₁ and R ₁₂ may be the same or different and each is an alkyl group (which may be substituted. Examples of the substituent include an alkoxy group and a phenoxy group. Specific examples of the substituent include Represents an ethoxy group, a 2,5-di (t) butylphenoxy group), and Q ₁ and Q ₂ represent a benzo condensed ring and a naphtho condensed ring, respectively. L represents a methine group, and X ₂ represents an anion. p represents an integer of 1 or 2, and represents 1 when forming an intramolecular salt. Specific examples of the filter dye represented by the general formula (S) include the compounds shown below, but the present invention is not limited thereto.

[0058]

[Chemical 8]

The photothermographic material used in the present invention basically has a photosensitive silver halide, a binder, and a dye-donating compound (which may also serve as a reducing agent as described later) on a support. It is a thing. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later. However, by incorporating a reducing agent in the light-sensitive material, the effect of promoting color image formation can be obtained.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having light sensitivity in different spectral regions is used. . 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 of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. The type of dye-donor compound (yellow, magenta, cyan) to be combined with each of these light-sensitive layers is arbitrary when reproducing a color image from image information converted into an electric signal, and is a conventional color light-sensitive material. There is no such restriction.

The photothermographic material comprises 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.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide, but is preferably 30. Silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing less than mol% of silver iodide.

The silver halide emulsion used in the present invention may be either 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 an optical fogging. Further, so-called multi-structured particles having different halogen compositions inside and inside the particle may be used. Of the multi-structure grains, those having a double structure are sometimes called a core-shell emulsion.

The silver halide used in the present invention is preferably a multi-structure grain, and a core-shell emulsion is more preferable. However, the present invention is not limited to this.

The silver halide emulsion used in the present invention is preferably a monodisperse emulsion and is disclosed in JP-A-3-110555.
The coefficient of variation described in No. 20 is preferably 20% or less.
More preferably 16% or less, further preferably 10%
It is the following. However, the present invention is not limited to this monodisperse emulsion.

The average grain size of the silver halide grains used in the present invention is 0.1 μm to 2.2 μm, preferably 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be cubic, octahedral, tabular with a high aspect ratio, potato-like, or any other. A cubic emulsion is more preferred.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,012, Research Disclosure (hereinafter abbreviated as RD) 17029 (197).
8 years), any of the silver halide emulsions described in JP-A No. 62-25159 can be used.

In the process of preparing the silver halide emulsion of the present invention, when a so-called desalting step of removing excess salt is carried out, as a means for this purpose, gel washing of gelatin which has been known for a long time is carried out by Nudell washing. Inorganic salts composed of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin derivatives (such as aliphatic acylated gelatin, aromatic compounds) may be used. A precipitation method (flocculation) using acylated gelatin, aromatic carbamoylated gelatin, etc. may be used. Preferably, a precipitation method using a compound represented by a precipitation agent (a) or a precipitation agent (b) described later is used, but the present invention is not limited thereto. An ultrafiltration method may be used without using any of the above-mentioned settling agents. The removal of 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,
Moreover, you may use it in combination of 2 or more type. The addition amount 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 added to the particles, or may be localized on the surface or inside of the particles.

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 core-shell emulsion, iridium may be added to the core and / or shell. As the compound, K ₂ IrC
I ₆ and K ₃ IrCl ₆ are 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.

The addition amount of iron used in the present invention is preferably 10 ^-7 to 10 ^-3 mol, and more preferably 10 ^-6 to 10 ^-3 mol, per mol of silver halide.

A part or all of these heavy metals is previously doped into 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 silver halide grains, rhodan salts, NH ₃ and thiourea compounds are used as silver halide solvents, organic thioether derivatives described in JP-B-47-11386 or JP-A-53-144319. Sulfur-containing compounds and the like can be used.

Nitrogen-containing compounds as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added in the step of forming silver halide grains. .

Gelatin is advantageously used as a protective colloid used in the preparation of 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 hydroxyethyl cellulose, cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly -N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, bulletin, and society of gelatin.
The Scientific, Photography of Japan (Bull.Soc.Sci.Phot., Japan), No16: Page
30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

For other conditions, see the graph
(P.Glafkides), "Chemie et Physique Photographique"
[Published by Paul Montel, 1967),
GF Duffin, Photographic Emulsion Chemistry
Emulsion Chemistry) "(The Focal Press Th
e Focal Press, 1966), VL Zelikman et al, "Making and Coating Photographic Emulsion" (The Focal Press, 196).
4 years) and the like. Ie the acidic method,
Either the neutral method or the ammonia method may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or 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 form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled or double jet method can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124, US Pat. No. 3650757).

During or after grain formation, the surface of the silver halide grain may be replaced with halogen which forms a hardly soluble silver halide grain.

The reaction solution may be stirred by any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily. Preferred pH
Range of 2.2 to 6.0, more preferably 3.0 to 5.
It is 5.

It consists of silver halide grains described in JP-A-5-119429, which has a phase with a high silver iodide content on the grain surface, and is chemically sensitized before desalting and addition of iodide ions. A silver halide emulsion can also be used.

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 hemioxonol dyes. It

Specifically, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978), pages 12 to 13 and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing action by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (see, for example, US Pat. No. 3615641, JP-A-6
3-23145 etc.).

In the present invention, in any of the above addition methods, the total addition amount of the sensitizing dye may be added at one time,
Also, it may be added in several divided 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 may be added at any time basically. That is, at the beginning of silver halide emulsion grain formation (may be added before nucleation), during or after formation, or at the beginning, during or after the desalting step, during gelatin redispersion, and It is before, during or after chemical sensitization, or at the time of preparing a coating solution. It is preferably added during or after the formation of silver halide grains or before or after the chemical sensitization. The addition after the chemical sensitization is to add the sensitizing dye after all the chemicals necessary for the chemical sensitization are added at the same temperature as the chemical sensitization.

It may be present in the reaction system of a soluble silver salt (eg silver nitrate) and a halide (eg potassium bromide) before the silver halide grains are formed as described in US Pat. No. 4,183,756. U.S. Pat. No. 42
As described in No. 25666, it may be present in the above reaction system after nucleation of silver halide grains and before completion of the silver halide grain formation step. A sensitizing dye may be present in the reaction solution at the same time as the formation of silver halide grains, that is, at the same time when the silver salt and the halide are mixed. It is more excellent in storage stability and gradation under high temperature conditions.

Concentration of additive liquid, solvent, time of addition (addition at once or addition over time), temperature, pH
May be any condition. Further, it may be added on the liquid surface or in the liquid. These conditions are described in JP-A 3-1
It is described in detail in No. 10555.

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

The sensitizing dye used in the emulsion of the present invention may be those described in, for example, JP-A-3-296745 and 4-31854.

The amount of the sensitizing dye to be used is suitably about 10 ^-8 to 10 ^-1 mol per mol of silver halide used in the production of emulsion.

Further, in the present invention, JP-A-63-2 is used.
The compounds represented by formula (A) on pages 3 to 5 of JP 3145 and specific examples thereof can be used together with a sensitizing dye. This compound is often used for supersensitization, improvement of storability, and suppression of change in sensitivity of coating solution over time. A light-sensitive material that has been spectrally sensitized in the infrared region of 750 nm or more may have even more effective effects. However, in some cases, it may have the effect of lowering the sensitivity.

The above compounds are known compounds as supersensitizers for sensitizing dyes in general light-sensitive materials for wet development processing (US Pat. No. 2875058, US Pat. No. 3,695,888, JP-A-59). No. 192242 and JP-A-59-191032), and a compound known as a supersensitizer in a heat-developable color light-sensitive material (see JP-A-59-180550).

Details and specific examples of the above compounds are described in JP-A-63 / 1988.
No. 23145.

The silver halide emulsion used in the present invention is
Although it can be used without being chemically sensitized, it is preferable to use one that has been chemically sensitized to increase the sensitivity. 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 and tellurium, and chemical sensitization with a noble metal such as palladium and iridium may be combined with the above chemical sensitization.

Also, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound typified by (1, 3, 3a, 7) -tetraazaindene is also preferably used. The preferred range of addition is silver halide 1
It is 10 ⁻¹ to 10 ⁻⁵ mol per mol.

The pH during chemical sensitization is preferably 5.3 to.
It is 10.5, and more preferably 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur capable of reacting with active gelatin or silver, such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid. ,
Rhodan, mercapto compounds and the like are used. Others, US Pat. Nos. 1,574,944 and 2,410,689
Nos. 2278947, 2728668, 3656955 and the like 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.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9).

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

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 4,483,914, columns 30-31, 4,33.
0,617, 4,590,152, JP-A-60-
140335, pages (17)-(18), ibid. 57-4.
0245, 56-138736, 59-178.
No. 458, No. 59-53831, No. 59-18244.
No. 9, No. 59-182450, No. 60-119555.
No. 60-128436 to No. 60-128439
No. 60-198540, No. 60-18174
No. 2, No. 61-259253, No. 62-244044.
No. 62-131253 to 62-131256
No. 78 to 9 of EP 220,746A2
There are reducing agents and reducing agent precursors described on page 6 and the like.

Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide, an electron transfer agent and / or
Alternatively, electron transfer agent precursors can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols.

The diffusion resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the light-sensitive material.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.01 to 20 moles, and particularly preferably 0.1 to 1 mole of silver.
10 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. A volatile compound is contained.

As an example of the dye-donating compound that can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers are described in T.W. H. J
by Ames, “The Theory of the P”
photographic Process "Fourth Edition 29
Pages 1-334 and 354-361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) n-Z represents a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (4). The following items (1) to (4) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide. To form a negative dye image).

US Pat. 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 developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. . Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479 and isoxazolones described in US Pat. No. 4,199,354. Examples of the compound include a compound that releases a diffusible dye by an intramolecular rewinding reaction of the ring.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used.

Examples thereof include US Pat. No. 4,139,
389, 4,139,379, JP-A-59-18.
Compounds which release diffusible dyes by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107.
JP-A-59-101649 and 61-88257.
, RD24025 (1984) and the like, which release a diffusible dye by an electron transfer reaction in the molecule after reduction, West German Patent No. 3,008,588A,
JP-A-56-142530, U.S. Pat. No. 4,343,
893, 4,619, 884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, electron acceptors described in US Pat. No. 4,450,223, etc. Nitro compounds, which later release diffusible dyes,
Examples thereof include compounds described in US Pat. No. 4,609,610 which release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220,746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,7.
83 to 396, compounds (1) to (3),
(7) to (10), (12), (13), (15),
(23) to (26), (31), (32), (35),
(36), (40), (41), (44), (53)-
(59), (64), (70), Public Technical Report 87-619
9 are compounds (11) to (23) and the like.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent Nos. 1,330,524, Japanese Patent Publication No. 48-39165, and U.S. Patent Nos. 3,443,940, 4,474,867.
No. 4,483,914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312 and 4,053,312,
4,055,428, 4,336,322, JP-A-59-65839, 59-699839, 5
No. 3-3819, No. 51-104343, RD174.
65, US Pat. Nos. 3,725,062 and 3,72.
8,113, 3,443,939, JP-A-58-
116537, 57-179840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the aforementioned U.S. Pat. No. 4,500,62.
The compounds described in Columns 22 to 44 of No. 6 can be mentioned. Among them, compounds (1) to (3), (10) to (13), (16) to (1
9), (28) to (30), (33) to (35), (3
8)-(40) and (42)-(64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 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 bound (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
5, 957, Research Disclosure, 19
1976, pp. 30-32, etc.), leuco dyes (U.S. Pat. Nos. 3,985,565, 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layers of the photographic material by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of binder.

JP-B-51-39853, JP-A-51-
The dispersion method using a polymer described in 59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (38)
The surfactants listed on the page can be used.

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

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (3)
2) to (41), the mordants described in JP-A-62-244.
No. 043, No. 62-244036, etc. can be mentioned. Also, U.S. Pat. No. 4,463,07
A dye-accepting high molecular compound as described in No. 9 may be used.

If necessary, the dye fixing element may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (U.S. Pat. No. 3,352,6
No. 81), benzophenone compounds (JP-A-46-
2784) and others, JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
1, 155, 4, 245, 018, columns 3 to 36,
No. 4,254,195, columns 3 to 8, JP-A-62-1.
74741, 61-88256 (27) to (2
9) page 63-199248, JP-A-1-7556.
There are compounds described in No. 8, No. 1-74272 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light-sensitive material. As an example, K. Veenkataraman
Chapter "The Chemistry of Synthe"
tic Dyes "Vol. V, Chapter 8, JP-A-61-143
Examples thereof include the compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used for the constituent layers of the light-sensitive material and the dye-fixing element, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving peelability. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444, JP-A-62-135826 and the like, oil-like fluorinated compounds such as fluorinated oil, or solid fluorinated compound resins such as tetrafluoroethylene resin Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. The matting agent can be used not only for the purpose of preventing adhesion, controlling slipperiness, and preventing Newton's rings, but also for making the surface of the dye fixing element (image surface) non-glossy.

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

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

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 4,51.
1, 493, JP-A-62-65038 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to enhance the storage stability of the light-sensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, 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), The compounds that generate a base by electrolysis as described in JP-A No. 61-232451 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are
It is advantageous to add them separately to the light-sensitive material and the dye fixing element.

In the present invention, various development terminators can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development terminating agent" as used herein means that after proper development,
It is a compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. For more details, see JP-A-62-253159.
No. (31) to (32).

In the present invention, the support for the dye-fixing element is one that can withstand the processing temperature. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A No. 62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or an enlarger, copying Method of scanning and exposing the original image through slits using the exposure light source of the machine, method of exposing image information by emitting light from a light emitting diode, various lasers, etc. via electric signals, image information of CRT, liquid crystal display, electroluminescence There is a method of outputting to an image display device such as a display or a plasma display and exposing it directly or through an optical system. Specifically, JP-A-2-129625,
The exposure methods described in Japanese Patent Application Nos. 3-338182, 4-0093388 and 4-281442 can be used.

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used.

[0163]

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 Photosensitive Layer)] Aqueous solutions having the compositions shown in Table 1 and (I) and (II) having the compositions shown in Table 2 were stirred well. Solution) was added simultaneously over 13 minutes, and 10 minutes later, Solution (III) and Solution (IV) having the compositions shown in Table 2 were added over 33 minutes.

[0166]

[Table 1]

[0167]

[Table 2]

[0168]

[Chemical 9]

Further, from 13 minutes after the addition of the solution III was started, and 27 minutes later, 150 cc of a 0.35% aqueous solution of the sensitizing dye (1) was added.
Was added.

[0170]

[Chemical 10]

After washing with water and desalting (precipitation agent a was used at a pH of 4.1) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 3. The yield of the obtained emulsion is 6
It was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2% at 30 g and an average grain size of 0.20 μm.

[0172]

[Table 3]

[0173]

[Chemical 11]

[0174]

[Chemical 12]

[0175]

[Chemical 13]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 5 were added to an aqueous solution having the composition shown in Table 4 and well stirred. ) Solution is added simultaneously over 18 minutes, and 10 minutes after that, solution (III) and (I) having the composition shown in Table 5 are added.
Solution V) was added over 24 minutes.

[0177]

[Table 4]

[0178]

[Table 5]

After rinsing with water and desalting (pH was set to 3.9 using the precipitating agent b) by a conventional method, calcium-depleted lime-treated ossein gelatin (calcium content: 150 PPM) was used.
22 g) and redispersed at 40 ° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added, pH is 5.9 and pAg is 7. 8
Adjusted to. Then, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 6. At the end of chemical sensitization, sensitizing dye (2),
(3) as a methanol solution (solution having the composition shown in Table 7)
Was added. Further, after the chemical sensitization, the temperature was lowered to 40 ° C., 200 g of a gelatin dispersion of stabilizer (1) described later was added, and the mixture was stirred well and then stored. The yield of the obtained emulsion is 938 g.
A monodisperse cubic silver chlorobromide emulsion with a coefficient of variation of 12.6%
The average particle size was 0.25 μm.

[0180]

[Chemical 14]

[0181]

[Table 6]

[0182]

[Chemical 15]

[0183]

[Table 7]

[0184]

[Chemical 16]

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

[0186]

[Table 8]

[0187]

[Table 9]

After washing with water and desalting (the precipitation agent a was used at pH 3.8) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and pAg to 7.8. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 10. The yield of the obtained emulsion was 680 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0189]

[Table 10]

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

To a well-stirred aqueous solution having the composition shown in Table 11, the solution having the composition shown in Table 12 was added over 24 minutes. After that, the precipitate was washed with water using a precipitating agent a, and then 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02μm and the yield is 512g.
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0192]

[Table 11]

[0193]

[Table 12]

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

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

[0196]

[Table 13]

[0197]

[Chemical 17]

[0198]

[Chemical 18]

[0199]

[Chemical 19]

[0200]

[Chemical 20]

[0201]

[Chemical 21]

[0202]

[Chemical formula 22]

[0203]

[Chemical formula 23]

[0204]

[Chemical formula 24]

[0205]

[Chemical 25]

A gelatin dispersion of reducing agent (2) was prepared according to the formulation in Table 14. That is, each oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersion was carried out at 00 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0207]

[Table 14]

[0208]

[Chemical formula 26]

[0209]

[Chemical 27]

A gelatin dispersion of stabilizer (1) was prepared according to the formulation in Table 15. That is, each oil phase component was 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, and then mixed with a homogenizer for 10 minutes at 10000 r.
dispersed at pm. Water was added to this and stirred to obtain a uniform dispersion.

[0211]

[Table 15]

[0212]

[Chemical 28]

[0213]

[Chemical 29]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 16. That is, after mixing and dissolving each component, a glass mill with an average particle size of 0.75 mm
Acid separated for a minute. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.
The one having a thickness of 25 μm was used. )

[0215]

[Table 16]

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

A photothermographic material 100 shown in Table 17 was prepared using the above materials.

[0218]

[Table 17]

[0219]

[Table 18]

[0220]

[Chemical 30]

[0221]

[Chemical 31]

[0222]

[Chemical 32]

[0223]

[Chemical 33]

[0224]

[Chemical 34]

Next, a method for producing the photosensitive material 101 will be described.

The method for preparing the organic silver salt (1) will be described. Gelatin 28g and benzotriazole 13.2g in water 30
It was dissolved in 0 ml. This solution was kept at 40 ° C. and stirred.
A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes. After that, a precipitating agent b was added to adjust the pH to cause precipitation, and excess salt was gradually added. Then, the pH was adjusted to 7.5 to obtain 400 g of a benzotriazole silver emulsion and an organic silver salt (1).

The combination of removing the dye (a) in the third layer and the first layer of the light-sensitive material 100 and using an organic silver salt, the light-sensitive material 100 as shown in Table 19 was used.
~ 104, 110, 111 were created.

[0228]

[Table 19]

Using these light-sensitive materials and Fuji PG Film Co., Ltd. paper PGSG for Fujix Pictography 3000, the sensitivity and fog of the light-sensitive materials and the life-time of the light-sensitive materials were evaluated.

[0230] As for the life stability, 50 times without forced aging and 50 times with no forced aging.
Samples that had been stored at 60 ° C. for one week were prepared and used.

Regarding sensitivity and fog, after exposure was carried out using an exposure system using the optical system shown in FIG. 2 of Japanese Patent Application No. 4-281442 as shown in Table 20, instead of the donor of Fujix Pictograph 3000. The light-sensitive materials 100 to 104, 110, 11 with and without forced aging described above.
1 was used and developed under standard conditions without exposure.

[0232]

[Table 20]

The processed samples thus obtained were measured for yellow, magenta and cyan sensitivities and fog with a self-recording densitometer. The sensitivity was evaluated by the reciprocal of the exposure amount (logarithmic unit, relative value) at which the density of fog plus 1.0 was obtained.

The above results are summarized in Table 21.

[0235]

[Table 21]

From the results shown in Table 21, the light-sensitive material of the present invention 10
1 to 103 and 111 are comparative photosensitive materials 100 and 10
It can be seen that this is an excellent light-sensitive material having higher sensitivity and less fog than those of Nos. 4 and 110.

[Procedure amendment]

[Submission date] March 4, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

By the way, it is known that fog (heat fog) unexpectedly occurs in normal wet development particularly in the development of a photothermographic material. In order to prevent this, various organic compounds called antifoggants are used, but these have the effect of reducing the sensitivity. Further, as described in JP-A-4-243256, a light-sensitive material using a paper support has a lower cost than using a polymer film (such as polyethylene terephthalate), and the light-sensitive material can be easily discarded. Although it has the advantage that it is present, it has the drawback that thermal fog is likely to occur. In order to improve this, it is necessary to use a large amount of antifoggant, and thus it is difficult to increase the sensitivity.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

On the other hand, it is known to use an organic silver salt such as silver benzotriazole in a photothermographic material. For example, JP-B-5-54107 shows that a high maximum concentration can be obtained by using 0.01 to 1.0 mol of an organic silver salt (organic silver salt oxidizing agent) per mol of silver halide. ing. However, Tokuhei 5-5
The invention described in No. 4107 is to use an organic silver salt in the same layer as a silver halide emulsion in a method of forming an image in a substantially water-free state. Also,
In the above-mentioned JP-A-4-243256, in the image forming method using a small amount of water as in the present invention, the amount of the organic silver salt used in the heat-developable photosensitive material using a paper support is changed to the total amount of silver halide. It is described that when the amount is less than 1 mol% with respect to the content, fog, variation in sensitivity, and raw storability are improved. However, JP-A-4-24325
The invention of No. 6 also describes the effect when an organic silver salt is contained in the same layer as silver halide. Furthermore, JP-A-1-
No. 100177, in the description of the invention of the method for producing an organic silver salt, it is described that the layer to which the organic silver salt is added may be the same layer as the silver halide or an adjacent layer.
It has never been shown to be particularly effective when using a paper support. Further, Japanese Patent Publication No. 48900/1993 describes that an organic silver salt is contained in an intermediate layer in order to prevent color turbidity, but thermal development containing an organic silver salt in the same layer as silver halide. It is an invention in image formation limited to color light-sensitive materials.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

[0020]

[Chemical 3]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The following compounds may be mentioned as specific examples of the compound represented by the general formula (III), but the present invention is not limited to the following examples.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

[0056]

[Chemical 7]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0235

[Correction method] Change

[Correction content]

[0235]

[Table 21]

Claims (4)

[Claims] 1. A heat-developable color light-sensitive material comprising at least a light-sensitive silver halide, a dye-donor substance, and a binder on a paper support, wherein the light-sensitive silver halide-containing layer contains substantially organic silver. A heat-developable color light-sensitive material characterized by containing an organic silver salt in at least one layer containing no light-sensitive silver halide and containing no salt. 2. The heat-developable color photosensitive material according to claim 1, wherein at least one of the photosensitive silver halides is spectrally sensitized so as to have a maximum value of spectral sensitivity at 750 nm or more. material. 3. The heat-developable color light-sensitive material according to claim 1, further comprising a non-diffusible filter dye having an absorption maximum at 700 nm or more. 4. The photothermographic material according to claim 1, wherein the non-diffusible filter dye is a compound represented by formula (S). [Chemical 1] [In the formula, R ₁₁ and R ₁₂ may be the same or different and each represents an alkyl group. Q ₁ and Q ₂ each represent a benzo condensed ring or a naphtho condensed ring. L represents a methine group, X
₂ ^- represents an anion. p represents an integer of 1 or 2,
When forming an intramolecular salt, p represents 1. ]