JPH05241267A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the heat-developable photosensitive material high in sensitivity and small in fog by sensitizing at least one kind of photosensitive silver halide with a tellurium compound. CONSTITUTION:The heat-developable photosensitive material formed on a support comprises the photo sensitive silver halide, a reducing agent, a binder, and a dyestuff donor, and at least one kind of silver halide is tellurium sensitized to obtain a maximum spectral sensitivity in a wavelength region of >=700nm, and the tellurium sensitizer is embodied by colloidal tellurium and telluro-uras, such as allyltelluroureas, N,N-dimethvl telluroureas, tetramethyltelluroureas, N-carboxyethyl-N',N'-dimethyl-telluroureas, and N,N'- dimethylethylenetelluroureas, isotellurocyanate, such as allylisotellurocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to an excellent photothermographic material having high sensitivity and less fog.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver photography (ed. 1982, Corona Publishing Co., Ltd., pages 242-255). Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. 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.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, 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 made to coexist with a reducing agent or a precursor thereof, and the reducing agent is added by thermal development according to the exposure amount of silver halide. 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. Further, in European Patent Publication No. 220746A and Kokai Giho No. 87-6199 (Vol. 12, No. 22), as a compound that releases a diffusible dye by a similar mechanism, an N—X bond (X is an oxygen atom, a nitrogen atom or sulfur) is disclosed. Photothermographic color photographic materials are described which use compounds which release diffusible dyes by the reductive cleavage of (representing atoms).

Such a photothermographic material requires a development process of 5
Since it is performed at 0 ° C. or higher, there is a problem that the silver halide is easily fogged by thermal fog. It is generally known that an antifoggant is used to prevent this fog. However, although the use of the antifoggant certainly suppresses the fog, there is a new problem that the sensitivity is lowered. Further, in a photothermographic material having a wavelength of maximum spectral sensitivity in a region of 700 nm or more, when spectral sensitization is performed, there is a problem that intrinsic desensitization occurs due to the sensitizing dye used and the sensitivity decreases. ..

In order to recover these reductions in sensitivity, the grain size of the photosensitive silver halide is generally increased, but this method causes fog sensitization. There has been a long-felt demand for a method of obtaining high sensitivity without increasing the grain size of photosensitive silver halide and further suppressing the increase of fog.

Specific methods include reduction sensitization using a reducing agent, noble metal sensitization using gold or the like, and chalcogen sensitization, which are used alone or in combination. Calicogen sensitization is a general term for sulfur sensitization, selenium sensitization, and tellurium sensitization. Sulfur sensitization and selenium sensitization have been studied very well in detail, whereas tellurium sensitization is Little known. That is, regarding the tellurium sensitization method and the tellurium sensitizer, US Pat.
499, 3,320,069, 3,772,0
No. 31, No. 3,531,289, No. 3,655,39
No. 4, 4,704,349, British Patent No. 235,2.
No. 11, No. 1,121,496, No. 1,295,46
No. 2, No. 1,369,696, No. 2,160,993
No., Canadian Patent No. 800,958, JP-A-61-67
Although disclosed generally in 845 etc., a detailed and specific description of tellurium sensitization is given in British Patent Nos. 1,295,462, 1,396,696 and Canadian Patent 800. No. 958 is known.
The use of sensitizing dyes in tellurium-sensitized emulsions
For example, although it is suggested in US Pat. No. 3,655,394, there is no specific description.

Specific effects when used in a photothermographic material such as the present invention, and specific effects when a sensitizing dye is used, which is inevitable when used in a color photosensitive material, 700
It can be said that the specific effect when spectrally sensitized above nm was not known at all.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent photothermographic material having high sensitivity and less fog.

[0011]

[Means for Solving the Problems] The above-mentioned problems are as follows (1),
It was solved by the configuration of (2). (1) That is, in a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donor compound on a support, at least one of the photosensitive silver halides is sensitized with tellurium. A photothermographic material characterized by: (2) The photothermographic material according to (1), wherein at least one of the photosensitive silver halides sensitized with tellurium has a wavelength of maximum spectral sensitivity in a region of 700 nm or more.

The present invention will be described in detail below.

The tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320.
069, 3,772,031, British Patent No. 23
No. 5,211, No. 1,121,496, No. 1,29
5,462, 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Ch.
em. Soc. Chem. Commun. ) 635 (1
980), ibid 1102 (1979), ibid
645 (1979), Journal of Chemicals.
Society Perkin Transaction (JC
hem. Soc. Perkin Trans. ) 1,2
It is preferable to use the compounds described in 191 (1980) and the like.

Specific tellurium sensitizers include colloidal tellurium and telluroureas (eg allyl tellurourea,
N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N,
N'-diphenylethylene tellurourea), isotellocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide, N, N-dimethyl tellurobenzamide), tellurohydrazide. (For example, N, N ′, N′-trimethyltelurobenzhydrazide), telluroester (for example, t-butyl-t-hexylteluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl). Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (eg negatively charged tellurides described in British Patent 1,295,462). On-containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate)
Etc.

Specific known tellurium sensitizers include colloidal tellurium and potassium telluride exemplified in Canadian Patent No. 800,958, which are commonly used in the art. It has an excellent aspect such as higher arrival sensitivity than sulfur sensitization. However, since the former is prepared by using a strong reducing agent such as stannous chloride, it hardly remains as a sensitizer with good reproducibility due to its residual or slight changes in the preparation conditions, and the latter potassium telluride. The compound itself has poor stability, is difficult to handle, and has poor reproducibility. Therefore, it is less preferable to use these tellurium sensitizers in the present invention. Among the above-mentioned tellurium compounds, the general formulas (I) and (II) shown in the following chemical formulas 1 and 2 are preferable.

[0016]

[Chemical 1]

Wherein R ₁ , R ₂ and R ₃ are aliphatic groups,
Aromatic group, heterocyclic group, OR ₄ , NR ₅ (R ₆ ), S
It represents R ₇ , OSiR ₈ (R ₉ ) (R ₁₀ ), X or a hydrogen atom. R ₄ and R ₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₅ and R ₆
Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₈ , R ₉ and R ₁₀ represent an aliphatic group, and X represents a halogen atom.

[0018]

[Chemical 2]

In the formula, R ₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group or --NR ₁₃ (R ₁₄ ), and R ₁₂ represents --NR ₁₅ (R
_16), - represents a _{N (R 17) N (R} 18) R 19 or -OR _20. R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Here, R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁
And R ₁₈ , R ₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R _18, and R ₁₃ and R ₂₀ may combine to form a ring.

Next, the general formula (I) will be described in detail.

In the general formula (I), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀
The aliphatic group represented by is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
Cyclopentyl group, cyclohexyl group, allyl group, 2-
Butenyl group, 3-pentenyl group, propargyl group, 3-
Examples thereof include a pentynyl group, a benzyl group and a phenethyl group.

In the general formula (I), R ₁ , R ₂ ,
The aromatic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms. And examples thereof include a phenyl group and a naphthyl group.

In the general formula (I), R ₁ , R ₂ ,
The heterocyclic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a base. These may be monocyclic or may form a condensed ring with other aromatic ring or heterocycle. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group and a benzimidazolyl group.

In the general formula (I), the cation represented by R ₄ and R ₇ represents an alkali metal or ammonium.

The halogen atom represented by X in the general formula (I) is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The aliphatic group, aromatic group and heterocyclic group may be substituted. The following are mentioned as a substituent.

Representative substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups,
Acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, Imido group, alkylthio group, arylthio group, halogen atom,
Examples thereof include a cyano group, a sulfo group, a carboxy group, a hydroxy group, a phosphono group, a nitro group, and a heterocyclic group.
These groups may be further substituted.

When there are two or more substituents, they may be the same or different.

R ₁ , R ₂ and R ₃ may combine with each other to form a ring with the phosphorus atom, and R ₅ and R ₆ may combine with each other to form a nitrogen-containing heterocycle. Good.

In the general formula (I), R ₁ , R ₂ and R ₃ preferably represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

Next, the general formula (II) will be described in detail.

In the general formula (II), R ₁₁ , R ₁₂ , R
_The aliphatic group represented by ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms. It is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group. Alkyl group, alkenyl group, alkynyl group,
Examples of the aralkyl group include a methyl group, an ethyl group, n
-Propyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3 -Pentynyl group, benzyl group, and phenethyl group.

In the general formula (II), R ₁₁ , R ₁₂ , R
_The aromatic group represented by ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ preferably has 6 to 30 carbon atoms, and particularly has 6 to 20 carbon atoms. It is a monocyclic or condensed ring aryl group, and examples thereof include a phenyl group and a naphthyl group.

In the general formula (II), R ₁₁ , R ₁₂ , R
_The heterocyclic group represented by ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ is a 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Is a saturated or unsaturated heterocyclic group. These may be monocyclic or may form a condensed ring with other aromatic ring or heterocycle. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group and a benzimidazolyl group.

In the general formula (II), R ₁₃ , R ₁₄ and R
_The acyl group represented by ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ is preferably an acyl group having 1 to 30 carbon atoms, and particularly a straight chain or branched acyl group having 1 to 20 carbon atoms. And examples thereof include an acetyl group, a benzoyl group, a formyl group, a pivaloyl group, and a decanoyl group.

Here, R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁ and R ₁₈ , R ₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R
_{When 18} and R ₁₃ and R ₂₀ combine to form a ring, examples thereof include an alkylene group, an arylene group, an aralkylene group, and an alkenylene group.

Further, the aliphatic group, aromatic group and heterocyclic group may be substituted with the substituents described in the general formula (I).

In the general formula (II), preferably R ₁₁ represents an aliphatic group, an aromatic group or --NR ₁₃ (R ₁₄ ) and R ₁₂ represents --NR ₁₅ (R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Represents an aliphatic group or an aromatic group.

In the general formula (II), more preferably R ₁₁ represents an aromatic group or --NR ₁₃ (R ₁₄ ) and R ₁₂ is --NR.
Represents ₁₅ (R ₁₆ ). R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an alkyl group or an aromatic group. Here, it is more preferable that R ₁₁ and R ₁₅ and R ₁₃ and R ₁₅ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

The general formulas (I) and (I
Specific examples of the compound represented by I) are shown in Chemical formulas 3 to 11 below, but the present invention is not limited thereto.

[0041]

[Chemical 3]

[0042]

[Chemical 4]

[0043]

[Chemical 5]

[0044]

[Chemical 6]

[0045]

[Chemical 7]

[0046]

[Chemical 8]

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

The compounds represented by the general formulas (I) and (II) of the present invention can be synthesized according to the already known methods. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 196.
9, 2927; Journal of Organometallic Chemistry (J. Organomet. Che.
m. ) 4,320 (1965); ibid, 1,200
(1963); ibid, 113, C35 (197
6); Phosphorus Sulfur (Phosphor)
us Sulfur) 15, 155 (1983); Chemist Ber. 109, 29.
96 (1976); Journal of Chemical Society Chemical Communication (J. Che.
m. Soc. Chem. Commun. ) 635 (19
80); ibid, 1102 (1979); ibid,
645 (1979); ibid, 820 (1987);
Journal of Chemical Society Perkin Transactions (J. Chem. Soc. Perk
in. Trans. ) 1,191 (1980);
Chemistry of Organo Selenium and
Tellurium Campounds (The Chemistr
y of Organo Selenium andT
ellurium Compounds) Volume 2 216
~ 267 (1987).

In the heat-developable color light-sensitive material of the present invention, basically, a photosensitive silver halide, a reducing agent, a binder and a dye-donating compound (which may also serve as a reducing agent as described later) are formed on a support. In addition, an organic metal salt oxidizing agent and the like can be added if necessary. These components are often added to the same layer,
If it is in a state where it can react, it can be divided and added to another layer. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.
The reducing agent is incorporated in the photothermographic material, and further, for example, by a method of diffusing from a dye fixing element described later,
You may use together the method supplied from the outside.

By thus incorporating the 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 sensitive to different spectral regions is used. .. For example, there are 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. 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 photothermographic material may be provided with various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer, in addition to the above-mentioned protective layer.

The silver halide emulsion (emulsion containing photosensitive silver halide) in the present invention may have various shapes. Examples of these are cubes, octahedra,
Examples thereof include regular particles having regular crystals such as tetradecahedron, tabular particles, spherical particles, particles having an irregular crystal shape such as potato particles, and the like.

As the silver halide composition of the grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride is used. Good, but
Silver bromide or silver chlorobromide is preferred. Further, it may contain silver thiocyanate, silver cyanate and the like.

The silver halide composition in the grain may be uniform, may have different halogen compositions inside and outside, or may have a layered structure (JP-A-57).
-154232, 58-108533, 58-
248469, 59-48755, 59-52.
237, U.S. Pat. Nos. 3,505,068 and 4,4.
33,048, 4,444,877, European Patent 100,984, and British Patent 1,027,146.
issue).

The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 3 μm.

Here, the monodisperse silver halide emulsion means that the total weight or the total number of silver halide grains contained therein is 95.
% Or more is within ± 40% of the average particle size, more preferably ± 3
Defined to be within 0%.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or a light fogging.

In the present invention, two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and they can be used in different emulsion layers and / or in the same emulsion layer. It is possible to use.

In particular, tabular silver halide grains have already been reported in US Pat. Nos. 4,434,226 and 4,4.
39,520, 4,414,310, 4,43
3,048, 4,414,306, 4,45
9,353, JP-A-59-99433, 62-2.
No. 09445 discloses the production method and use technique.

Further, JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocations are intentionally introduced.

The ratio of the average grain diameter to the average grain thickness in tabular grains (hereinafter referred to as grain diameter / thickness) is preferably 2 or more, preferably 3 to 12, and particularly 5
It is preferably -8.

The grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains. A simple method is to use the average diameter of all tabular grains and the average thickness of all average grains. It can also be obtained as a ratio with.

The tabular grains have a diameter (corresponding to a circle) of 0.3 μm or more, preferably 0.3 to 10 μm, and more preferably 0.
5 to 5.0 μm, more preferably 0.5 to 2.0 μm
Is.

The grain thickness is less than 1.0 μm, preferably 0.05 to 0.5 μm, more preferably 0.08 to
It is 0.3 μm.

In the present invention, the tabular grains account for 50% or more of the projected area of all grains in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more.

The grain diameter and grain thickness of tabular grains can be measured by electron micrographs of grains as described in US Pat. No. 4,434,226.

Specific examples of the halogen composition of the tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide and silver chloroiodobromide. Silver bromide or silver chlorobromide is preferred. It may also contain silver thiocyanate, silver cyanate and the like.

Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

In the tabular grains, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver thiocyanate and oxides. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395,478, No. 4,433,501
Issue 4,463,087, Issue 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

The silver halide grains used in the present invention are
Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.
hysique Photographique, Pa
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .. 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 in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the above regular grains can be obtained by controlling the pAg and pH during grain formation. For details, see, for example,
Science and Engineering (Photog
radical Science and Engine
ering), Volume 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521.
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

During the production of emulsions containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Patent No. 3,67
2,900, 3,650,757, 4,24
No. 2,445, JP-A Nos. 55-142329 and 55-
The description of No. 158124 and the like can be referred to.

To accelerate the ripening of silver halide grains,
Silver halide solvents are useful. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, introduction of a silver halide solution into the reactor can accelerate ripening. Other ripening agents can be used, and the total amount of these ripening agents can be mixed in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. It is also possible to add a halide salt, a silver salt or a deflocculant, and to introduce them into the reactor. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. In addition, JP-A-53-8
It is also possible to use thione compounds as disclosed in 2408 and 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The properties of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 1977.
As described on pages 19 to 27, the silver halide emulsion can reduce-sensitize the inside of the grain during the precipitation formation process.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are:
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
No. 36, JP-A No. 62-253159 and Daffin's "Photographic Emulsion Chemistry", pages 138-143 (published by Focal Press, 1966).

The silver halide grains used in the present invention are
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. Additives used in such a process are Research Disclosure No. 17643 and N
o. 18716.

It is advantageous to use gelatin as the protective colloid used when the emulsion of the present invention is prepared, but other 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, carboxymethyl cellulose, cellulose sulfates; sodium alginate, starch derivatives and the like. Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-processed gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 2-9, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, polopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,25
7, JP-A-59-180550 and JP-A-60-1403.
No. 35, RD17029 (1978) pages 12 to 13 and the like.

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

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (see, for example, US Pat. Nos. 3,615,641 and JP-A-63-23145).

The time when these sensitizing dyes are added to the emulsion may be during chemical ripening or before and after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after nucleation. In particular, the presence of a sensitizing dye at the time of chemical sensitization often gives a preferable effect.

The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,1.
No. 97, No. 3,713, 828, No. 3, 615, 64
No. 3, No. 3,615, 632, No. 3,617, 293
Nos. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,632,349, No. 3,677,765
No. 3,370,449, No. 3,770,440
No. 3, ibid. 3,769,025, ibid. 3,745,014
Nos. 3,713,828 and 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ^{3 to} 10 g / m ^{3 in} terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include those described in US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver. Various antifoggants or photographic stabilizers can be used in the present invention.
As an example, RD17643 (1978) 24-
Azoles and azaindenes described on page 25, JP-A-5
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-9-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-8.
The acetylene compounds described in 7957 are used.

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 by itself but exhibits a 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, 44
No. 83, col. 30, columns 31-43617;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96, 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, 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 electron transfer agent or the precursor thereof has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3-
It is a pyrazolidone or an aminophenol.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents that do not substantially move in the layer of the photosensitive element.
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 0.001 to 20 mol, and particularly preferably 0.1 to 20 mol per mol of silver.
It is from 01 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound which produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. It may also contain a sex compound.

Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) which forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. This nondiffusible group may form a polymer chain. Specific examples of color developers and couplers are TH James
"The Theory of the Photographic Process" Fourth Edition 2
91-334 pages, and 354-361 pages, JP-A-58.
-123533, 58-149046, 58-
149047, 59-11148, and 59-1
24399, 59-174835, 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye imagewise. 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 corresponds to a photosensitive silver salt having an imagewise latent image. Or, conversely, causes a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or D
ye is released, and the released Dye and (Dye-Y) n-
Z represents a group having a property of causing a difference in diffusibility from Z, n 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 (1) to (4). The following items (1) to (5) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and "and" are the diffusible dye image (corresponding to the development of silver halide). To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, and 3544545.
No. 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. 4,053,137, a non-diffusible compound which releases a diffusible dye under 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 US Pat. No. 4,199.
Compounds that release a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354, etc.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example thereof, US Pat. No. 4,13,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107, JP-A-59
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, US Pat. Nos. 4,343,893 and 4619.
Compounds which release a diffusible dye by cleavage of a single bond after reduction as described in US Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223 and the like that release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 and the like that release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having a —X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, SO ₂ —X (where X is as defined above) in one molecule described in JP-A-1-26842. Compounds having electron-withdrawing group, JP-A-63-271344
Compounds having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-27.
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 1341.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2
(3), (7) to (10), (12), (13), (15), (23) to (26), (3
1), (32), (35), (36), (40), (41), (44), (53) to (5
9), (64), (70), compound (1) of open technical report 87-6199
1) to (23).

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 No. 1330524, Japanese Patent Publication No. 48-39165, US Patent Nos. 3443940, 4474867, and 448.
3914 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 any other 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, 40,53312, and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113, and 3,443.
939, JP-A-58-116537, and JP-A-57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44, among which the compounds (1) to (3) described in the U.S. Pat. (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

Other than the above-mentioned couplers and dye-providing compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pages 54 to 58). , Etc., azo dyes used in the heat-development silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
Year 4 issue, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617, etc.) and the like can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion-resistant reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

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, especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
A 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 as a binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. The 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 photosensitive element or may be applied on the same support as the photosensitive element. Regarding the relationship between the light-sensitive element 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.

In order to include such a form in which the light-sensitive element and the dye-fixing element are coated on the same support as described above, the light-sensitive material of the present invention will be referred to as the light-sensitive element hereinafter for the sake of convenience. explain. The dye fixing element is also called a dye fixing material.

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, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 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.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye-fixing element. As an example thereof, pages (26) to (2) of JP-A-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, natural compounds such as polysaccharides such as starch, gum arabic, dextran and 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 1
It is preferably 20 g or less per m ² , particularly 10 g or less, more preferably 7 g or less.

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

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of promoting the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, it is 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. 45114.
93, 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 element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210660 and a compound (referred to as a complex forming compound) capable of forming a complex reaction with a metal ion constituting the sparingly soluble metal compound, JP-A-61-2
The compounds that generate a base by electrolysis described in No. 32451 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

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

The term "development terminator" as used herein means, after proper development,
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. More specifically, JP-A-62-25315
No. 9 (31) to (32).

The constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element are 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. ..

In the constituent layers of the light-sensitive element and the dye-fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" technical material P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective.

The silicone oils described in JP-A Nos. 62-215953 and 63-46449 are also effective.

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind.

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.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A-54-48535 and JP-A-62-
There are compounds described in Nos. 136641 and 61-8256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
55, 42425018, columns 3 to 36, 4,25.
4,195, columns 3 to 8, JP-A-62-174741.
No. 61-88256, pages (27) to (29), JP-A-1-75568, JP-A-62-31096, JP-A-1.
There are compounds described in, for example, No. -74272.

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

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

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

A fluorescent whitening agent may be used in the light-sensitive element 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 element. As an example, K. Veenkataraman edited by "The Chem
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based carboxy compounds.

The fluorescent whitening agent can be used in combination with an anti-fading agent.

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

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

A matting agent can be used in the light-sensitive element and the dye-fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A No. 61-88256, pages (26) to (32).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and synthetic film made by polypropylene or the like. Blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass and the like 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 to these, the supports described in JP-A-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 element, 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, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on the photosensitive element,
As described above, US Patent No. 4 of natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and the crystallization is possible, but especially about 80 ° C. to about 180 ° C.
℃ is effective. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but especially 50 ° C.
Above all, it is more preferable that the temperature is lower by about 10 ° C. than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer.

Further, JP-A-59-218443 and JP-A-6-218443.
As described in detail in No. 1-238056 and the like, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method,
The heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator.).
Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used.
Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to a dye fixing element, a light sensitive element or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Alternatively, the solvent may be contained in a microcapsule or the like in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive element or the dye-fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer.

Examples of hydrophilic thermal solvents are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.

As the heating method in the developing and / or transferring step, a heated block or plate may be contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. may be contacted. Or passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and the resistance heating element layer may be energized for heating. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye-fixing element,
For the pressure condition and the method of applying the pressure for the close contact, see Japanese Patent Laid-Open No.
The method described in page 1-147244 (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259
The device described in No. 44 etc. is preferably used.

[0176]

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

Example 1 A method for preparing a zinc hydroxide dispersion will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant,
0.5 g of anionic surfactant (1) was added to a 5% aqueous gelatin solution, and the mixture was milled for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.4 μm.

[0181]

[Chemical 12]

[0182]

[Chemical 13]

Next, the method for preparing the dye trapping agent dispersion will be described.

Polymer latex (A) (solid content 13
%) 108 ml, surfactant (2) 20 g, and water 1232 ml with stirring, while stirring anionic surfactant (3) 5
% Aqueous solution 600 ml was added over 10 minutes. Using the ultrafiltration module, the dispersion thus prepared was
It was concentrated to 0 ml and desalted. Next, 1500 ml of water was added, and the same operation was repeated once more to disperse the dye trapping agent dispersion 5
00g was obtained.

[0185]

[Chemical 14]

[0186]

[Chemical 15]

[0187]

[Chemical 16]

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

Gelatin dispersions of cyan, magenta, yellow and electron donor were prepared according to the formulations shown in Table 1. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, this solution and the water phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed.
Dispersed at 00 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0190]

[Table 1]

[0191]

[Chemical 17]

[0192]

[Chemical 18]

[0193]

[Chemical 19]

[0194]

[Chemical 20]

[0195]

[Chemical 21]

[0196]

[Chemical formula 22]

[0197]

[Chemical formula 23]

[0198]

[Chemical formula 24]

[0199]

[Chemical 25]

[0200]

[Chemical formula 26]

[0201]

[Chemical 27]

[0202]

[Chemical 28]

[0203]

[Chemical 29]

[0204]

[Chemical 30]

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

Light-Sensitive Silver Halide Emulsion (1) [For Red-Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 3 in 480 ml of water).
g and 30 mg of the chemical (A) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) shown in Table 2 were added simultaneously at the same flow rate for 25 minutes. Also, 10 minutes after the start of addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of a pigment (containing 1 g of gelatin, 67 mg of pigment (a), 133 mg of pigment (b), 4 mg of pigment (c) in 105 ml of water) (Incubated at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0208]

[Chemical 31]

[0209]

[Table 2]

[0210]

[Chemical 32]

[0211]

[Chemical 33]

[0212]

[Chemical 34]

Light-Sensitive Silver Halide Emulsion (2) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 783 ml of water).
solution (I) and solution (II) shown in Table 3 were simultaneously added to each of the same at a constant flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) shown in Table 3 were simultaneously added at an equal flow rate for 15 minutes. Two minutes after the addition of the solutions (III) and (IV) was started, an aqueous solution of a gelatin dispersion of a dye (0.9 g of gelatin in 95 ml of water, 61 mg of the dye (a),
Then, 121 mg of the dye (b) and 4 mg of the dye (c) and kept at 50 ° C.) were added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0215]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide and 4 g of sodium chloride in 675 ml of water).
g and 15 mg of the chemical (A) were added and kept at 48 ° C.), the solutions (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 20 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of a gelatin dispersion of the dye (3.0 g of gelatin in 120 ml of water, 30 parts of the dye (d)) was added.
(Containing 0 mg and kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0218]

[Table 4]

[0219]

[Chemical 35]

Light-Sensitive Silver Halide Emulsion (4) [For Green-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 675 ml of water, 0.3 g of potassium bromide, 6 parts of sodium chloride).
solution (I) and solution (II) shown in Table 5 were simultaneously added to the above solution at a constant flow rate for 20 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 5 were added simultaneously at the same flow rate for 20 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of a gelatin dispersion of the dye (2.5 g of gelatin in 95 ml of water, 250 parts of the dye (d)) was added.
which contained mg and was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.42 μm was obtained.

[0222]

[Table 5]

Light-Sensitive Silver Halide Emulsion (5) [For Blue-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 675 ml of water, 0.5 g of potassium bromide, 4 parts of sodium chloride).
solution (I) and solution (II) shown in Table 6 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 6 were added simultaneously at the same flow rate for 32 minutes. One minute after the addition of solutions (III) and (IV) was completed, 220 mg of dye (e) and 110 mg of dye (f) were added to an aqueous solution of dye (in 95 ml of water and 5 ml of methanol).
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene was added for optimum chemical sensitization at 68 ° C. Thus, monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm
35 g were obtained.

[0225]

[Table 6]

[0226]

[Chemical 36]

[0227]

[Chemical 37]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (gelatin 20 g, potassium bromide 0.3 g, sodium chloride 9 in 675 ml of water).
solution (I) and solution (II) shown in Table 7 were simultaneously added to the above solution at a constant flow rate for 10 minutes. After 10 minutes, solution (III) and solution (IV) in Table 7 were added simultaneously at the same flow rate for 30 minutes. Also (III), (IV)
One minute after the addition of the solution was completed, 150 mg of dye (e) and 75 mg of dye (f) were dissolved in 66 ml of water and 4 ml of methanol.
Which was kept at 60 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0230]

[Table 7]

A light-sensitive material 1 shown in Table 8 using the above-mentioned materials
I made 01.

[0232]

[Table 8]

[0233]

[Table 9]

[0234]

[Table 10]

[0235]

[Chemical 38]

[0236]

[Chemical Formula 39]

[0237]

[Chemical 40]

[0238]

[Chemical 41]

[0239]

[Chemical 42]

[0240]

[Chemical 43]

[0241]

[Chemical 44]

Photosensitive Silver Halide of Photosensitive Material 101 (1)
In (6), sodium thiosulfate used for chemical sensitization was replaced with tellurium sensitizer shown in Table 11, and emulsions different in that they were optimally chemically sensitized were used to prepare light-sensitive materials 102 to 106. Had made.

[0243]

[Table 11]

Next, a method of making an image receiving material will be described.

Image-receiving material R101 having a constitution as shown in Table 12
made.

[0246]

[Table 12]

[0247]

[Table 13]

[0248]

[Chemical 45]

[0249]

[Chemical 46]

[0250]

[Chemical 47]

[0251]

[Chemical 48]

[0252]

[Chemical 49]

[0253]

[Chemical 50]

[0254]

[Chemical 51]

[0255]

[Chemical 52]

[0256]

[Chemical 53]

[0257]

[Chemical 54]

[0258]

[Chemical 55]

Using the above-mentioned photographic materials 101 to 106 and image receiving material R101, processing was carried out using the image recording apparatus described in Japanese Patent Application No. 63-137104. That is, the original image [a test chart in which Y, M, Cy, and gray wedges of which the density is continuously changing is recorded] is scanned and exposed through a slit, and the exposed light-sensitive material is exposed to water kept at 40 ° C. Four
After soaking for a second, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface temperature becomes 80 ° C., the photosensitive material is peeled off from the image receiving material by heating for 15 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

Table 14 shows the results of measuring the maximum density and the relative sensitivity of the thus-obtained image in the gray area by using a self-recording densitometer. The relative sensitivity is expressed by the relative value (true number) of the exposure amount at a density of 0.7,
The sensitivity of the comparative photosensitive material 101 is represented as 100.

[0261]

[Table 14]

As is clear from the results in Table 14, the light-sensitive material of the present invention has high sensitivity and high maximum density. still,
In this light-sensitive material, the low fog of silver halide appears as the highest density. Example 2 A method for preparing the emulsion (7) will be described. (Emulsion for Fifth Layer) Solution I and solution II having the composition shown in Table 16 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 15 which was well stirred, and then the composition shown in Table 16 was added. Liquid III and IV 3
Added over 5 minutes.

[0263]

[Table 15]

[0264]

[Table 16]

From 18 minutes after the start of addition of the liquid III,
0.5% methanol solution of sensitizing dye (a) over 7 minutes
5 cc was added. Washing with water, desalting (pH =
4.1), then add 22 g of gelatin and adjust the pH.
= 6.0, pAg = 7.9, and then chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are shown in Table 17. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.31 micrometer.

[0266]

[Table 17]

The method for preparing the emulsion (8) will be described. (Emulsion for third layer) Solution I and solution II having the composition shown in Table 19 were simultaneously added over 10 minutes to an aqueous solution having the composition shown in Table 18 which was well stirred, and then the emulsion having the composition shown in Table 19 was added. Solution III and IV solution 4
Added over 5 minutes.

[0268]

[Table 18]

[0269]

[Table 19]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent a at pH = 3.9), gelatin 1 was used.
After 2 g was added to adjust pH = 5.9 and pAg = 7.8, chemical sensitization was performed at 70 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of sensitizing dye (b) (gelatin 5%, sensitizing dye 0.5%) was added. The compounds used for the chemical sensitization are shown in Table 20. The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.32 micrometer.

[0271]

[Table 20]

The method for preparing the emulsion (9) will be described. (Emulsion for First Layer) Solution I and solution II having the composition shown in Table 22 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 21, which was well stirred, and then the composition shown in Table 22 was added. Solution III and IV solution 2
Added over 5 minutes.

[0273]

[Table 21]

[0274]

[Table 22]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent a at pH = 3.8), gelatin 2 was used.
After adjusting to pH = 6.6 and pAg = 8.0 by adding 0 g, chemical sensitization was performed at 58 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of sensitizing dye (c) (5% gelatin, 1% sensitizing dye) was added. The compounds used for the chemical sensitization are shown in Table 23. The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.22 micrometer.

[0276]

[Table 23]

Next, a method for preparing a gelatin dispersion of the dye-donor compound will be described. Magenta dye-donor compound (A) 14.64 g, reducing agent A 0.8 g, antifoggant 0.20 g, surfactant 0.4 g, high boiling organic solvent (2) 5.1 g Then, 70 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 71 g of this solution and a 14% solution of lime-processed gelatin and 220 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. This dispersion is referred to as a dispersion of a magenta dye-donor compound. 7.3 g of cyan dye-donor compound (B1), cyan dye-donor compound (B1)
2) 10.6 g, reducing agent A 1.0 g, antifoggant shown in [Chemical Formula 14] 0.30 g, and surfactant 0.
4 g of the high-boiling organic solvent (2) was weighed, 9.8 g of the high-boiling point organic solvent (2) was weighed, 40 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 71 g of a 14% solution of lime-processed gelatin and 260 cc of water were mixed by stirring, and then dispersed by a homogenizer for 10 minutes at 10,000 rpm. This dispersion is referred to as a dispersion of a cyan dye-donor compound. 18.8 g of a yellow dye-donor compound (C), 1.0 g of a reducing agent A, 0.13 g of an antifoggant, 1.5 g of a surfactant,
Weigh 2.1 g of dye a and 7.5 g of high boiling point organic solvent (2), add 45 ml of ethyl acetate, heat and dissolve at about 60 ° C.,
A uniform solution was obtained. 14 of this solution and lime-processed gelatin
% Solution 71 g and water 160 cc were mixed with stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a yellow dye-donor compound dispersion. With these, a photothermographic material 201 as shown in Table 24 was constructed. Table 26 shows the emulsions and the numbers of the light-sensitive materials used.

[0278]

[Table 24]

[0279]

[Table 25]

[0280]

[Table 26]

[0281]

[Chemical 56]

[0282]

[Chemical 57]

[0283]

[Chemical 58]

[0284]

[Chemical 59]

[0285]

[Chemical 60]

[0286]

[Chemical formula 61]

[0287]

[Chemical formula 62]

[0288]

[Chemical 63]

[0289]

[Chemical 64]

[0290]

[Chemical 65]

[0291]

[Chemical 66]

[0292]

[Chemical 67]

[0293]

[Chemical 68]

[0294]

[Chemical 69]

[0295]

[Chemical 70]

The high boiling organic solvent (1) is triisononyl phosphate, and the high boiling organic solvent (2) is trihexyl phosphate. A method for preparing a zinc hydroxide dispersion will be described. Average particle size is 0.15μ
12.5 g of zinc hydroxide of m, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the mixture was milled for 30 minutes using glass beads having an average particle size of 0.75 mm. did. The glass beads were separated to obtain a zinc hydroxide dispersion.

Photosensitive Silver Halide of Photosensitive Material 201 (7)
In (9), the sulfur sensitizers used in the chemical sensitization are replaced with the tellurium sensitizers shown in Table 26, and emulsions different in that they are optimally chemically sensitized are used.
I made 06. Next, how to make the dye fixing material will be described. Table 27 on polyethylene laminated paper support
A dye fixing material was prepared by applying the composition.

[0298]

[Table 27]

The compounds used in Table 27 are shown below.

[0300]

[Chemical 71]

[0301]

[Chemical 72]

[0302]

[Chemical formula 73]

[0303]

[Chemical 74]

The polymer, high boiling point organic solvent, and matting agent are shown below. Polymer * 5 Sodium vinyl alcohol copolymer (75/25 molar ratio) Polymer * 7 Dextran (molecular weight 70,000) High boiling organic solvent * 8 Reofos 95 (Ajinomoto Co., Inc.)
Matting agent * 10 Benzoanamin resin (18 vol% of particles exceeding 10μ)

Next, evaluation was performed by the following exposure and processing. A tungsten light bulb is used as the above-mentioned light-sensitive material, and the density is continuously changed. R, IR1, IR2 three color separation filters (R is 650 to 690 nm, IR1 is 730 to 7).
70nm bandpass filter, IR2 is 790nm
The above-mentioned transmission filter is used. ) Through
Exposure was performed under the conditions shown in Table 28 using the laser exposure apparatus described in Japanese Patent Application Nos. 63-281418 and 63-204805. 11 ml / m ² of water was supplied to the exposed light-sensitive materials 201 to 206 by a wire bar, and then the layers were superposed so that the dye-fixing material was in contact with the film surface. Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 85 ° C., the dye fixing material was peeled from the photosensitive material after heating for 25 seconds, and an image was obtained on the dye fixing material.

[0306]

[Table 28]

Table 29 shows the results of measurement of the minimum density and relative sensitivity of the image in the gray portion thus obtained by measuring with a self-recording densitometer. The relative sensitivity is expressed by the relative value (true number) of the exposure amount at a density of 0.7,
The sensitivity of the comparative photosensitive material 201 is expressed as 100.

[0308]

[Table 29]

As is clear from the results in Table 29, the light-sensitive material of the present invention has low sensitivity and minimum density. still,
In this light-sensitive material, the low fog of silver halide appears as the minimum density.

[0310]

As described above, according to the present invention,
A photothermographic material having high sensitivity and low fog can be provided.

Claims (2)

[Claims] 1. In a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donating compound on a support, at least one of the photosensitive silver halides is tellurium-sensitized. A photothermographic material characterized by: 2. The photothermographic material according to claim 1, wherein at least one of the photosensitive silver halides sensitized with tellurium has a wavelength of maximum spectral sensitivity in a region of 700 nm or more.