JPH06347969A - Heat-developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance image density and yet to reduce fog and fluctuation of sensitivity at the time of changing development temperature by incorporating at least one of other compounds in the heat-developable color photosensitive material containing photosensitive silver halide, a specified compound, a binder, and a dye donor. CONSTITUTION:The heat-developable color photosensitive material comprises the photosensitive silver halide, at least one of the compounds represented by formulae I and II, the binder, and the dye donor and further contains at least one of the compounds represented by formulae III-a-III-g. In formulae I and II, Ball is an organic ballasting group capable of rendering this compound nondiffusive; Y is a C group necessary to complete a benzene or naphthalene ring; R<1> is optionally substituted alkyl or such cycloalkyl or the like; R<2> is H, halogen, or the like; and (n) is an integer of 0-5.

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, which has a particularly excellent image density, has a low fog when heat-developed, and has a sensitivity fluctuation when the development temperature is changed. It relates to less heat-developable color photosensitive materials.

[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 salt photograph edition (1982, published by Corona Publishing Co., Ltd.), pages 242 to 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.

A method of using the general formula (I) or (II) alone is described in JP-A-62-247358, and a method of using the general formula (III) alone is disclosed in Japanese Patent Publication No.
No. 13701, it is not sufficient to have an excellent image density in heat development, reduce fog, and reduce sensitivity fluctuation when the development temperature is changed. In the present invention, by incorporating the general formula (I) or (II) into the photosensitive silver halide and further using the general formula (III) in combination, excellent image density can be obtained, fog can be reduced, and development can be performed. We have succeeded in reducing the sensitivity fluctuation when the temperature is changed.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to have excellent image density in heat development, reduce fog, and reduce sensitivity fluctuation when the development temperature is changed, and To provide a heat-developable color light-sensitive material having excellent photographic characteristics.

[0007]

The object of the present invention is to provide a photosensitive silver halide having the general formula (I) or (II) on a support.
In a heat-developable color light-sensitive material having at least one compound represented by the formula (1), a binder, and a dye-donor compound which releases a diffusible dye corresponding to or against silver development, at least a compound of the general formula (III) It was achieved by a heat-developable color light-sensitive material characterized by containing one kind.

[0008]

[Chemical 4]

[In the general formulas (I) and (II), Bal
l represents an organic ballast group capable of rendering the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ball may be omitted. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ₁ is a substituted or unsubstituted alkyl group,
It represents a cycloalkyl group, an aralkyl group, an aryl group, an amino group or a heterocyclic group. R ₂ is a hydrogen atom, a halogen atom or a substituted or unsubstituted cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group Represents a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group. n represents an integer of 0 to 5, n
When ₂ is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring. In addition, when Y represents an atomic group necessary for completing the naphthalene nucleus, Ba
11 and R ₂ can be attached to any of the ring systems so formed. ]

[0010]

[Chemical 5]

In the general formulas (III-a) to (III-g),
A represents a divalent electron-withdrawing group, R ₁ is an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an anilino group, or a heterocyclic group. p is 1
Alternatively, it is an integer of 2. R ₂ represents an alkyl group, an alkoxy group, a hydroxyl group or halogen, and m is 0 to 4
Is an integer. Q represents a benzene ring or a hetero ring which may be condensed with the phenol ring. R ₃ is an alkyl group,
It represents an aryl group or a heterocyclic group. Y ₁ is an aryl group,
Alkyl group, heterocyclic group, -P (O) (Rb) -Ra group,
Alternatively, it represents a -C (O) -Ra group. R _'4 represents an alkylene group, arylene group or aralkylene group,
R ₄ represents an alkyl group or an aryl group. However, Y ₁ and R ₄ are not an alkyl group at the same time. Ra and Rb are an alkyl group, an aryl group, an amino group,
Represents an alkoxy group or an aryloxy group. n is 1
Represents an integer of ~ 5. R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a phenylsulfonyl group, or an acyl group. R ₆ represents the same substituent as R ₄ . R ₅ ,
R ₆ may be closed to form a 5- to 7-membered ring.
R ₇ and R ₈ represent the same substituents as R ₄ but are closed to form 5
Or, a 7-membered ring may be formed.

[0012]

[Chemical 6]

Represents a 5- to 7-membered heterocycle.

The present invention comprises a support, a photosensitive silver halide, a reducing agent, a general formula (I) or (II), a binder,
And a heat-developable color light-sensitive material having a dye-donating compound and containing at least one of the compounds of the general formulas (III-a) to (III-g). To have and reduce fog,
It is possible to reduce sensitivity fluctuation when the developing temperature is changed.

The heat-developable color light-sensitive material of the present invention comprises at least one layer containing a light-sensitive silver halide, a reducing agent, a compound represented by formula (I) or (II), a binder, and a dye-donating compound. The photosensitive layer has the general formula (III-a)
To (III-g) at least one of them is contained.

First, the general formulas (I) and (II) will be described in detail.

In the general formulas (I) and (II), R ₁ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. Preferred examples of R ₁ include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group and dodecyl group; substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, such as cyclohexyl. Group, etc .; substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, for example, benzyl group, β-phenethyl group, etc .; carbon number 6
A substituted or unsubstituted aryl group having from 30 to 30, such as a phenyl group, a naphthyl group, a tolyl group, a xylyl group, etc .; a substituted or unsubstituted amino group having from 0 to 30 carbon atoms, such as an amino group, a methylamino group, an isopropylamino group. , Cyclohexylamino group, phenylamino group, benzylamino group, N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diisopropylamino group, N, N
-Dicyclohexylamino group, N, N-diphenylamino group, N, N-dibenzylamino group; substituted or unsubstituted heterocyclic groups such as pyridyl group, furyl group and thienyl group.

The substituent of the aryl group will be described in detail. As the substituent, for example, a halogen atom (chlorine atom,
Bromine atom, etc.), amino group, alkoxy group, aryloxy group, carbonamido group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group, carboxy group, alkyl group (methyl group, ethyl group) Groups, propyl groups, etc.), acylamino groups, sulfamoyl groups, ester groups, alkylsulfonyl groups, alkylsulfonylamino groups, arylsulfonylamino groups, and the like.

R ₂ is a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryl It represents an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group.

Preferred examples of R ₂ are hydrogen atom; halogen atom such as bromine atom, chlorine atom, etc .;
20 substituted or unsubstituted alkyl groups, for example, methyl group, ethyl group, isopropyl group, t-butyl group and the like; substituted or unsubstituted cycloalkyl groups having 5 to 20 carbon atoms,
For example, cyclopentyl group, cyclohexyl group and the like; substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, such as benzyl group, β-phenethyl group and the like; substituted or unsubstituted aryl group having 6 to 20 carbon atoms, such as phenyl group, Naphthyl group and the like listed in R ₁ ; substituted or unsubstituted heterocyclic group, such as pyridyl group, furyl group, thienyl group, etc .; substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, such as methoxy group. , Butoxy group, methoxyethoxy group and the like; substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, for example, phenoxy group and the like; 1 to 20 carbon atoms
A substituted or unsubstituted acyl group such as acetyl group,
Balmitoyl group and the like; substituted or unsubstituted alkyloxycarbonyl group having 1 to 20 carbon atoms, such as methoxycarbonyl group; aryloxycarbonyl group having 1 to 20 carbon atoms, such as phenoxycarbonyl group and the like; carbon number 1 to 2
0 substituted or unsubstituted carbamoyl group, for example, methylcarbamoyl group, dimethylcarbamoyl group, diisopropylcarbamoyl group and the like; substituted or unsubstituted sulfamoyl group having 1 to 20 carbon atoms, for example, dimethylsulfamoyl group and the like; carbon number 1 ~ 20 substituted or unsubstituted alkylsulfonyl groups such as methylsulfonyl group;
A substituted or unsubstituted arylsulfonyl group having 1 to 20 carbon atoms, such as phenylsulfonyl group, p-methylphenylsulfonyl group and the like; a substituted or unsubstituted acylamino group having 2 to 20 carbon atoms, such as acetylamino group, N-
A methylacetylamino group, a palmitoylamino group, etc .; a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms,
For example, methylthio group, ethylthio group, etc .; C6-30
And a substituted or unsubstituted arylthio group such as phenylthio group and m-methoxycarbonylphenylthio group.

N represents an integer of 0 to 5, and when n is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring.

As such a ring, bicyclo [2.2.
1] Hept-2-ene, cyclohexene and the like.

Ball represents an organic ballast group capable of rendering the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ball may be omitted.

The nature of the ballast group (Ball) is not critical as long as the ballast imparts diffusion resistance to the compound. Common ballast groups are straight or branched straight chain alkyl groups that are directly or indirectly attached to the compound, and are either indirectly attached to or directly attached to the benzene nucleus. Benzene-based and naphthalene-based aromatic groups are included. Effective ballast groups are generally groups having a minimum of 8 carbon atoms.

For example, a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms, an acylamino group having 8 to 30 carbon atoms, an acyl group having 8 to 30 carbon atoms,
Acyloxy group having 8 to 30 carbon atoms, 8 to 8 carbon atoms
Examples thereof include an alkoxy group having 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, an alkoxy group having an alkoxycarbonyl group having 8 to 30 carbon atoms, and the like. In addition, as an example of indirect bonding, a carbamoyl group or a sulfamoyl group represented by the general formulas (IV) and (V) (a nitrogen atom contained in these groups is bonded to a ballast group) is used. What has been done is preferable.

[0026]

[Chemical 7]

In the general formulas (IV) and (V), R ₃ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (for example, a methyl group,
An ethyl group and the like), a cycloalkyl group (for example, a cyclohexyl group) and an aryl group (for example, a phenyl group) are preferable.

L represents a divalent group (for example, an alkylene group, a phenyl group, a divalent arylthio group, etc.), and m represents 0 or 1.

Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. In addition, when Y represents an atomic group necessary for completing the naphthalene nucleus, Bal
l and R ₂ can be attached to any of the ring systems so formed.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the compounds in the present invention are not limited to these.

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

The compounds of the present invention may be used alone or in combination of two or more kinds. And in the light-sensitive material, emulsion layer, intermediate layer,
Although it can be contained in any layer such as a protective layer,
It is particularly effective to add it to the dispersion of the dye-providing substance so that it is contained in the emulsion layer.

The addition amount is 0.0005 to 20 times mol, and particularly effective addition amount range is 0.001 to 4 times mol based on silver.

The above general formulas (III-a) to (III-g) will be described below. A in the general formula (III-a) is preferably

[0045]

[Chemical 19]

Represents an electron-withdrawing group represented by R _{1 to} R ₉ and Y in the above general formulas (III-a) to (III-g)
_1, R _'4, Ra, the alkyl group in Rb is a straight-chain, branched-chain alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, Shikuroarukishi group, a cycloalkenyl group,
The aryl group is a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, naphthyl group, etc.
Alkoxy groups are methoxy groups, ethoxy groups, benzyloxy groups, heterodecyloxy groups, octadecyloxy groups, etc., aryloxy groups are phenoxy groups, 2-methylphenoxy groups, naphthoxy groups, etc., alkylamino groups are methylamino groups, Butylamino group, octylamino group, etc.
Anilino groups phenylamino group, 2-chloroanilino group, a 3-dodecyloxy carbonyl anilino group, an alkylene group is a methylene group, an ethylene group, 1,10-decylene _{group, -CH 2 CH 2 OCH 2 CH} 2 - group , An arylene group is a 1,4-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, and the like, and an aralkylene group is

[0047]

[Chemical 20]

Etc., the heterocyclic group is a pyrazolyl group, an imidazolyl group, a triazolyl group, a pyridyl group, a quinolyl group,
It represents a piperidyl group, a triazinyl group and the like. Also R ₁ ~
Substituted alkyl group, substituted aryl group, substituted alkoxy group, substituted aryloxy group, substituted alkylamino group, substituted anilino group, substituted alkylene group, substituted arylene group, and substituted in R ₉ and Y ₁ , R ′ ₄ , Ra, and Rb. Aralkylene group, the substituent in the substituted heterocyclic group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, Sulfonyloxy group, acylamino group, anilino group, urend group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide Group, carbamoyl group Acyl group, a sulfamoyl group,
It represents a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Also the general formula
The heterocyclic group in (III-f) is the same as the above heterocyclic group, and may have the above substituent. Among the compounds represented by the general formulas (III-a) to (III-g), the general formulas (III-a) (III-b) (III-
d), more preferably the general formula
(III-d).

Specific examples of the compounds represented by formulas (III-a) to (III-g) are shown below, but the compounds in the present invention are not limited thereto.

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

The compounds represented by the general formulas (III-a) to (III-g) may be used alone or in combination of two or more kinds. It can be contained in any layer of the light-sensitive material such as an emulsion layer, an intermediate layer, a protective layer, etc., but it is particularly effective to add it to the dispersion of the dye-providing substance and to contain it in the emulsion layer. .

The addition amount is 0.001 to 20 times mol, and the particularly effective addition amount range is 0.005 to 2 times mol.

The photothermographic material used in the present invention basically has a photosensitive silver halide emulsion and a binder on a support, and further, if necessary, an organic metal salt oxidizing agent and a dye donating compound. (In some cases, the reducing agent also serves as described later) and the like. These components are often added to the same layer, but they may be added separately in different 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 it may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. . For example, JP-A-59-180,550 and JP-A-64-13,546, 6
2-253,159, European Patent Publication No. 479,167.
Combination of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer, infrared-sensitive layer combination, red-sensitive layer, infrared-sensitive layer (I), red There is a combination of the outer photosensitive layer (II). 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 as required, as described in JP-A-1-252954. In the heat-developable light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between the uppermost layer and the lowermost layer between the silver halide emulsion layers. It may be provided, and various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure as described in the above patent, US Pat. No. 5,051,33
An undercoat layer as described in JP-A No. 5-167,838
No. 6, intermediate layers having a solid pigment as described in JP-A-61-20943, JP-A-1-120553, 5-
Nos. 34,884 and 2-64,634, an intermediate layer containing a reducing agent or a DIR compound, US Pat.
17,454, 5,139,919, JP-A-2-
An intermediate layer having an electron transfer agent as described in JP-A No. 235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer combining these may be provided. The support is preferably designed to have an antistatic function and a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion which can be used in the present invention is
It may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Also,
It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halide having a different composition may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and the method of mixing the monodisperse emulsions and adjusting the gradation as described in JP-A-1-167,743 and 4-223,463 is preferably used. . The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is one having a regular crystal such as a cube, octahedron, or tetrahedron, a sphere, an irregular crystal system such as a flat plate having a high aspect ratio, or a twin plane. Any of those having such a crystal defect, a composite system thereof or the like may be used. Specifically, US Pat. No. 4,500,626
No. 50, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17,643 (December 1978), pages 22-23, No. 18,716 (1979).
Nov., 648, same No. 307, 105 (198)
Nov. 9, pp. 863-865, JP-A-62-253,
159, 64-13,546, JP-A-2-23.
No. 6,546, No. 3-110,555, and Graphide, "Physics and Chemistry of Photography", published by Pall Monte (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio
Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsion" by Zelikmann et al., published by Focal Press (V.
L. Zelikman et al., Making and Coating Photograph
Any of the silver halide emulsions prepared by the method described in icEmulsion, Focal Press, 1964) or the like can be used.

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

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

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thioether compound or JP-B No. 47-1 is used.
The organic thioether derivatives described in 1,386 or the sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
Tel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion).
Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (V.
L. Zelikman et al., Making and Coating Photograph
ic Emulsion, Focal Press, 1964) etc. may be referred to. That is, any of an acidic method, a neutral method and an ammonia method 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. The double jet method is preferably used to obtain a monodisperse emulsion. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. A so-called controlled double jet method, in which pAg in the liquid phase in which silver halide is produced is kept constant, can also be used as one type of the simultaneous mixing method.

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

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253,159). Further, an antifoggant described below can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
The method described in No. 0,446 can be used. The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and pAg is preferably 6.0.
˜10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

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

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

A hydrophilic binder is preferably used as the binder of the constituent layers of the photothermographic material and the dye fixing material. Examples thereof include Research Disclosure mentioned above and pages (71) to (75) of JP-A-64-13,546.
The thing described in the 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 synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymers. Also, U.S. Pat. No. 4,96
No. 0,681, JP-A No. 62-245,260 and the like, a superabsorbent polymer, that is, -COOM or -SO.
₃ Homopolymers of vinyl monomers having M (M is hydrogen atom or alkali metal) or copolymers of these vinyl monomers or copolymers with other vinyl monomers (eg 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. In particular, a combination of gelatin and the above binder is preferred. Gelatin may be selected from lime-processed gelatin, acid-processed gelatin, so-called decalcified gelatin having a reduced content of calcium, etc. according to various purposes. Is also preferable.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less, more preferably 10 g or less, and further preferably 7 g to 0.5 g per 1 m ² .

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 00,626, columns 52 to 53. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol of photosensitive silver halide.
-10 mol, preferably 0.01-1 mol can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² , preferably 0.1 to ⁴ g / m ² g in terms of silver.

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 reducing agents used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,839,272, No. 4,
330,617, 4,590,152, 5,0
17,454, 5,139,919, JP-A-60
-140,335, pages (17)-(18), ibid. 57.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181, 742, No. 61-259, 253.
No. 62-201, 434, and No. 62-244, 04.
No. 4, 62-131, 253, 62-131, 62
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
No. 2-234, 158, 3-160, 443
And EP-A-220,746, pages 78 to 96, and the like. 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, if necessary, an electron transfer agent and / or an electron transfer agent may be added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. Particularly preferably, said US Pat. No. 5,139,
919, European Patent Publication No. 418,743, JP-A-1
Those described in Nos. -138,556 and 3-102,345 are used. Further, a method of stably introducing into a layer as described in JP-A-2-230,143 and JP-A-2-235,044 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Sulfonamide phenols, sulfonamide naphthols, JP-A-53-
110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, and compounds described as electron donors, and a diffusion-resistant and reducing dye described later. Donor compounds and the like can be mentioned. Further, an electron donor precursor as described in JP-A-3-160,443 is also preferably used. Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixture, improving color reproduction, improving white background, and preventing silver transfer to the dye fixing material. Specifically, European Patent Publication No. 52
4,649, 357,040, Japanese Patent Laid-Open No. 4-24
No. 9,245, No. 2-64,633, No. 2-46,4
No. 50 and the reducing agents described in JP-A No. 63-186,240 are preferably used. In addition, Japanese Examined Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
Development inhibitor releasing reducing compounds such as those described in JP-A Nos. 2-64,634, 3-43,735 and EP-A-451,833 can also be used. In the present invention, the total amount of the reducing agent added is 0.01 to 20 mol per mol of silver,
It is particularly preferably 0.1 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. A sex compound is used. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers can be found in "The Theory of th" by TH James.
e Photographic Process "Fourth Edition, pages 291-334 and 354-361, RD-307, 105, 871.
Page, JP-A-58-123,533, 58-149,
046, 58-149, 047, 59-11.
1,148, 59-124,399, 59-1
74,835, 59-231,539, 59-
231, 540, 60-2, 950, 60-
No. 2,951, No. 60-14, 242, No. 60-2
3, 474, 60-66, 249 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) m-Y) _n- Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. Or (Dye) m corresponding to the photosensitive silver salt having a latent image in (dye) m-Y) _n- Z.
-Y is released, and the released (Dye) m-Y and ((Dy) m-Y
e) m-Y) _n- Z represents a group having a property of causing a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, and m and n Either one
If not, the plurality of Dyes 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 (3). In addition, the following items (1) to (5) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and is the diffusible dye image (positive dye image) corresponding 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 Japanese Patent Publication No. 3-68. No. 387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent No. 220,746A2, US Pat. No. 4,783,
No. 396, Open Technical Report 87-6, 199, JP-A-64-1
As described in JP-A-3,546, a non-diffusible compound which itself releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used. Examples thereof include US Pat. Nos. 4,139,389 and 4,139,
379, JP-A-59-185, 333 and 57-8.
Compounds that release a diffusible dye by a nucleophilic substitution reaction in the molecule after being reduced, as described in 4,453, etc.,
U.S. Pat. No. 4,232,107, JP-A-59-10
1,649, 61-88,257, RD24,0
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
142,530, U.S. Pat. No. 4,343,893,
Compounds that cleave a single bond after reduction to release a diffusible dye described in U.S. Pat. No. 4,619,884, and diffusibility after electron acceptance described in U.S. Pat. No. 4,450,223. Examples thereof include a nitro compound that releases a dye and a compound that releases a diffusible dye after electron acceptance as described in US Pat. No. 4,609,610.

Further, as more preferable ones, European Patent No. 220,746, Open Technical Report 87-6,199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201,6.
No. 53, No. 63-201, 654, No. 64-13, 5
No. 46, etc., a compound having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, one molecule described in JP-A-1-26,842. A compound having SO ₂ -X (where X is as defined above) and an electron-withdrawing group within the molecule, and a PO-X bond (where X is as defined above) within one molecule described in JP-A-63-271344. And a compound having an electron-withdrawing group, JP-A-63-271341
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. In addition, JP-A-1-161,237
The compounds described in JP-A No. 1-161, 342, which release the diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent 220,746.
Or the compounds (1) to (3), (7) to (10), (12), described in U.S. Pat. No. 4,783,396.
(13), (15), (23) to (26), (31),
(32), (35), (36), (40), (41),
(44), (53) to (59), (64), (70),
Compound (11) described in Published Technical Report 87-6,199
To (23), and compounds (1) to (84) described in JP-A No. 64-13,546.

A coupler having a diffusible dye as a leaving group, which is a non-diffusible compound itself (DDR coupler) which releases a diffusible dye by a reaction with an oxidized product of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-
39,165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 4,483,914. Reducible to silver halide or organic silver salt,
It itself is a non-diffusible compound (DRR compound) that releases a diffusible dye when it reduces the other party. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322, and JP-A-59-65,839. 59-69,839, 53-3,819, 51-104,343, RD
17,465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116,537, 57-179,840.
And U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626 in columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13),
(16)-(19), (28)-(30), (33)-
(35), (38) to (40) and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, 37th
The compounds described in columns 39 to 39 are also useful. In addition, as a dye-donating 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, 54
~ 58, etc.), azo dyes used in the heat-development silver bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, pages 30-32, etc.), leuco dyes (US Patent No. 3,985,565,
No. 4,022,617, etc.) can also be used. In the present invention, this DRR compound is particularly preferably used.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be incorporated into the layer of the photothermographic material by known methods such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
55,470, 4,536,466, 4,53
No. 6,467, No. 4,587, 206, No. 4,55
No. 5,476, No. 4,599,296, Japanese Examined Patent Publication 3-6
A high-boiling point organic solvent such as that described in No. 2,256 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the dye-donor compound used. Also, 1 cc or less per 1 g of binder, further 0.5 cc
Below, 0.3 cc or less is particularly suitable. See also
-39,853 and JP-A-51-59,943, dispersion methods using polymers and JP-A-62-30,2.
The method of adding a fine particle dispersion described in No. 42 etc. 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, Japanese Unexamined Patent Publication No. 59-157,636 (3)
The surfactants described in Research Disclosure, pages 7 to 38 can be used. In the photothermographic material of the present invention, a compound capable of activating development and stabilizing an image at the same time can be used. 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, for the purpose of improving the white background of the obtained image by immobilizing or achromaticizing unnecessary dyes and colored substances in the constituent layers of the photothermographic material of the present invention. Various compounds can be added. Specifically, European Published Patent No. 353,741
No. 461,416, JP-A-63-163,345.
No. 62-203,158 can be used.

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

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photothermographic material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used. Specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59, JP-A-61-161.
88, 256, pages (32) to (41) and JP-A-1-1.
No. 61,236, mordanting agents described on pages (4) to (7), U.S. Pat. Nos. 4,774,162 and 4,619,883.
Nos. 4,594,308 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. The hydrophilic binder is preferable as the binder used in the dye fixing material of the present invention. Further, it is preferable to use carrageenans as described in EP-A-443,529 and latexes having a glass transition temperature of 40 ° C. or lower as described in JP-B-3-74,820. If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, an undercoat layer, an intermediate layer, a back layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye fixing material, a high boiling point organic solvent can be used as a plasticizer, a slipping agent or an agent for improving the releasability between the photosensitive material and the dye fixing material. Specific examples include those described in Research Disclosure and JP-A-62-245,253. 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. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.

An anti-fading agent may be used in the photothermographic material and the dye fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a certain kind of metal complex, and the dye image stabilizer and the ultraviolet absorber described in the above Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61
The compounds described in No. 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- 2,784),
Other JP-A-54-48,535, 62-136,
641 and 61-88,256. Further, the ultraviolet absorbing polymer described in JP-A-62-260,152 is also effective. Examples of the metal complex include U.S. Patent Nos. 4,241,155 and 4,245,018.
No. 3 to 36 columns, No. 4,254,195 No. 3 to 8
Column, JP-A Nos. 62-174,741 and 61-88,2.
56 (27)-(29), 63-199, 248.
And JP-A Nos. 1-75,568 and 1-74,272.

The anti-fading agent for preventing the fading of the dye transferred to the dye fixing material may be contained in the dye fixing material in advance, or the dye may be externally applied from the photothermographic material or a transfer solvent described later. You may make it supply to a fixing material. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the photothermographic material and the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a photothermographic material or a transfer solvent. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. 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 or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers and fluorescent whitening agents are described in JP-A-62-215,27.
2 (125)-(137), JP-A-1-161,
No. 36, pages (17) to (43).

As the hardener used in the constituent layers of the photothermographic material and the dye fixing material, the above-mentioned Research Disclosure, US Pat. Nos. 4,678,739, column 41, 4,791,042, JP-A No. Sho 59-116,655
No. 62-245, 261, 61-18, 942.
And the hardeners described in JP-A-4-218,044 and the like. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.),
Examples thereof include N-methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234,157). These hardeners
0.001 to 1 g, preferably 0.005 to 0.5 g, is used per 1 g of coated gelatin. The layer to be added may be any layer of the photosensitive material and the dye-fixing material, or may be divided into two or more layers and added.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the photothermographic material and dye fixing material. Specific examples thereof include Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-62-13,546 (7). (9) page, (57) to (71) page and (8
1)-(97), U.S. Pat. No. 4,775,610,
No. 4,626,500, No. 4,983,494, JP-A Nos. 62-174,747, 62-239,148.
No. 63-264,747, JP-A-1-150,1.
No. 35, No. 2-110,557, No. 2-178,65
No. 0, RD17, 643 (1978) (24)-(2
5) The compounds described on page etc. are mentioned. These compounds are preferably used in an amount of 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

In the constituent layers of the photothermographic material and the dye fixing material, coating aids, improvement of peeling property, improvement of sliding property, antistatic property,
Various surfactants can be used for the purpose of promoting development and the like. Specific examples of the surfactant include Research Disclosure, JP-A Nos. 62-173,463 and 62-62.
No. 183,457. The constituent layers of the photothermographic material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-209 can be used.
No. 44, No. 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photothermographic material and dye fixing material for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. As the matting agent, in addition to the compounds described in JP-A-61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-2749.
44, and 63-274952.
In addition, the compounds described in the above Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer if necessary. In addition, the constituent layers of the photothermographic material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3.
-11,338, Japanese Patent Publication No. 2-51,496 and the like.

In the present invention, an image forming accelerator can be used in the photothermographic material and / or dye fixing material. 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 heat development sensitization. It has functions such as accelerating the migration of dyes from the material layer to the dye fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants. , And compounds that interact with silver or silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. As a base precursor, a salt of an organic acid and a base that is decarboxylated by heat, an intramolecular nucleophilic substitution reaction,
Examples include compounds that release amines by Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,
Nos. 514,493 and 4,657,848.

In a system in which heat development and transfer of a dye are simultaneously carried out in the presence of a small amount of water, a method of incorporating a base and / or a base precursor in a dye-fixing material is preferable in order to enhance the storage stability of the photothermographic material. . Besides the above,
European Patent Publication 210,660, US Pat. No. 4,74
No. 0,445, a combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. The compounds that generate a base by electrolysis described in 1) can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the photothermographic material and the dye fixing element as described in the above-mentioned patent.

In the present invention, various development stoppers can be used in the photothermographic material and / or the dye fixing material for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. . The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-6
2-253, 159 (31) to (32).

In the present invention, as the support for the photothermographic material and the dye fixing material, those capable of withstanding the processing temperature are used. Generally, papers and synthetic polymers (films) described in "Basics of Photographic Engineering-Silver Salt Photographs-" edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) (223) to (240) pages. ) And other photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, Film method synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass etc. Is used. These can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as required. In addition, JP-A-62-253,159 (29)-(31), JP-A-1-161,236 (14)-(17), JP-A-63-316,848
No. 2, JP-A-2-22651, and JP-A-3-56,955.
No. 5,001,033 and the like can be used. The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents. Specifically, JP-A-63-220,24
The support described in No. 6 can be used. Further, the surface of the support is preferably subjected to various surface treatments and undercoats for the purpose of improving the adhesion with the hydrophilic binder.

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

As a light source for recording an image on a photothermographic material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., US Pat. Kaihei 2-53,
The light source and the exposure method described in JP-A No. 378 and JP-A No. 2-54,672 can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), Inorganic compounds typified by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462 and JP-A-62-2104
The compound described in No. 32 is preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera, or the like, NTV signal standard (NT
For example, a television signal represented by SC), 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 or CAD can be used.

The photothermographic material and / or dye fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is disclosed in JP-A-61-114.
Those described in No. 5,544 can be used. The heating temperature in the heat development step is about 50 ° C to 250 ° C, and particularly about 60 ° C to 180 ° C is useful. The dye transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is particularly 50 ° C. or higher and about 10 ° C higher than the temperature in the heat development step.
Up to a temperature lower by ℃ is preferred.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056 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 system, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or the diffusion transfer of the dye include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases are referred to in the section of the image formation accelerator). Those described are used), or a low boiling point solvent or a mixed solution of a low boiling point solvent and water or the above basic aqueous solution. Further, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, an antifungal agent, and an antibacterial agent may be contained in the solvent. Water is preferably used as the solvent used in the steps of heat development and diffusion transfer, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water or the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up, or may be circulated and repeatedly used. In the latter case, water containing the components eluted from the material will be used. Further, JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
You may use the apparatus and water described in No. 5, etc.

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

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the photothermographic material and / or the dye fixing material can also be adopted. The layer to be incorporated may be any of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but a dye fixing layer and / or a layer adjacent thereto is preferable. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heating block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244 (page 27) can be applied to the method of superimposing the heat-developable light-sensitive material and the dye-fixing material.

Any of a variety of heat developing apparatus can be used to process the photographic elements of this invention. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, No. 62
-25,944, Japanese Patent Application Nos. 4-277,517 and 4
The devices described in No. 243,072, No. 4-244,693 and the like are preferably used. Further, as a commercially available apparatus, Pictrostat 100, Pictrostat 200, Pictrography 3000, Pictrography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1

How to make a photosensitive silver halide emulsion

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 2 g of sodium chloride in 600 ml of water).
g and 30 mg of the compound (a) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 1 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 1 were added simultaneously at the same flow rate for 25 minutes. Wash with water by the usual method,
After desalting, 22 g of lime-treated ossein gelatin and 90 mg of compound (b) were added to adjust pH to 6.2 and pAg to 7.7.
After adding 5 mg of ribonucleic acid degradation product and 2 mg of trimethylthiourea to the mixture and optimally chemically sensitizing at 60 ° C. for about 50 minutes,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 225 mg, dye (a) 64 mg, KBr 5
After sequentially adding 00 mg, the mixture was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm
35 g were obtained.

[0106]

[Table 1]

[0107]

[Chemical 27]

[0108]

[Chemical 28]

Photosensitive Silver Halide Emulsion (2) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 ml of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and 15 mg of the compound (a) were added and kept at 55 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 10 minutes, the solutions (III) and (IV) in Table 2 were further added.
The solution was added simultaneously at an equal flow rate for 20 minutes. Also (III), (I
One minute after the end of the addition of the solution V), an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 95 ml of water, 180 mg of the dye (b))
Which was kept at 45 ° C.) was added all at once. Washed with water and desalted by a conventional method, and then lime-treated ossein gelatin 2
PH was adjusted to 6.0 and pAg was adjusted to 7.6 by adding 0 g, and sodium thiosulfate 1 mg and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 47 mg and chloroauric acid 0. 6 mg was added for optimum chemical sensitization at 68 ° C., and then 165 mg of antifoggant (1) was added, followed by cooling.
Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0110]

[Table 2]

[0111]

[Chemical 29]

Photosensitive Silver Halide Emulsion (3) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of KBr, 2 g of NaCl, 15 mg of compound (a) in 630 ml of water were added to give 75). (Solution kept at 0 ° C.), solution I and solution II having the compositions shown in Table 3 were added, and after 30 seconds, solution II was added over 30 minutes each, and 5 minutes after the completion of addition of solution II.
Solution III was added, and 30 seconds after that, solution IV was added over 30 minutes each. Then, solutions III and IV having the compositions shown in Table 3 were added over 35 minutes. Thereafter, 19 cc of a 1N solution of sodium hydroxide was added for neutralization to adjust the pH of the solution to 6. Then, add 1.4 mg of sodium thiosulfate, and add 3
After that, 1.2 mg of chloroauric acid was added and the mixture was kept at 75 ° C. for 60 minutes. Then, a solution prepared by dissolving 430 mg of dye (c) in 80 cc of methanol was added, and 5 minutes after that, the temperature was lowered to 35 ° C.

Thereafter, the solution v was added over 5 minutes.
Then, after washing with water and desalting by a conventional method (performed with 1 g of the precipitating agent (a) at pH 3.9), 6 g of lime-treated ossein gelatin and 68 mg of the antifoggant (2) were added to adjust the pH to 6. It was set to 0. pAg is 8.5, electric conductivity is 40
It was 00 μS. The silver halide grains of the resulting emulsion were octahedral and the grain size was 0.4 μm.

[0114]

[Table 3]

[0115]

[Chemical 30]

[0116]

[Chemical 31]

[0117]

[Chemical 32]

A method for preparing a zinc hydroxide dispersion will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Cyan dye-donor compound (A
1) 7.3 g, cyan dye-donor compound (A2) 10.6 g, compound (D) 0.25 g, surfactant (1) 0.8 g, high boiling organic solvent (1) 7 g 3 g of the high boiling point organic solvent (2) was weighed, 50 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 80 cc of water were mixed by stirring, and then the mixture was mixed with a homogenizer for 10 minutes for 1,000 minutes.
Dispersed at 0 rpm. After the dispersion, 180 cc of water for dilution was added. This dispersion is called a cyan dye-donor compound dispersion.

[0120]

[Chemical 33]

[0121]

[Chemical 34]

[0122]

[Chemical 35]

[0123]

[Chemical 36]

1 magenta dye-donor compound (B)
4.93 g, compound (D) 0.21 g, surfactant (1) 0.384 g, high boiling point organic solvent (1) 7.4.
g was weighed, 50 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 100 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes.
Then, 120 CC of dilution water was added. This dispersion is referred to as a dispersion of the magenta dye-donor compound.

[0125]

[Chemical 37]

1 of the yellow dye-donor compound (C) was used.
8.8 g, compound (E) 3.8 g, surfactant (1)
Was weighed in an amount of 1.74 g and the high boiling organic solvent (2) was weighed in an amount of 9 g, 50 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 73 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After that, 105 cc of water for dilution was added. This dispersion is called a yellow dye-donor compound dispersion.

[0127]

[Chemical 38]

[0128]

[Chemical Formula 39]

10 g of reducing agent (A) and surfactant (1)
3 g, high boiling organic solvent (1) 6.3 g, ethyl acetate 16
g was dissolved by heating at 60 ° C. to obtain a uniform solution. This solution was mixed with 71.4 g of 14% acid-treated gelatin and 70.6 g of water, added to the solution kept at 55 ° C., stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a reducing agent dispersion.

[0130]

[Chemical 40]

By these, the photothermographic materials 101 shown in Tables 4 and 5 were constructed.

[0132]

[Table 4]

[0133]

[Table 5]

[0134]

[Table 6]

[0135]

[Chemical 41]

[0136]

[Chemical 42]

[0137]

[Chemical 43]

[0138]

[Chemical 44]

Next, a method for producing the image receiving material will be described. An image receiving material R201 having a constitution as shown in Table 7, Table 8 and Table 9 was prepared.

[0140]

[Table 7]

[0141]

[Table 8]

[0142]

[Table 9]

[0143]

[Chemical formula 45]

[0144]

[Chemical formula 46]

[0145]

[Chemical 47]

[0146]

[Chemical 48]

[0147]

[Chemical 49]

[0148]

[Chemical 50]

[0149]

[Chemical 51]

Preparation of Photosensitive Material 102 When a dispersion of a magenta dye-donor compound was prepared, compound (III-d-5) was added together with the dye-donor compound at 6.7 g.
A dispersion was made in the same manner except that it was added. When preparing a dispersion of a cyan dye-donor compound, the compound (III
A dispersion of a cyan dye-donor compound was prepared in the same manner except that 6.5 g of -d-5) was added. Except for these, the same material as the photosensitive material 101 was used. Similarly,
Photosensitive materials 103 to 110 shown in Table 10 were prepared. The compounds shown in Table 10 such as the compounds of the present invention were added in the amounts corresponding to the coating amounts shown in Table 10 when preparing dispersions of each dye-donor compound.

[0151]

[Table 10]

Next, the above light-sensitive materials 101 to 110 were exposed and processed as follows. Using a tungsten bulb, B.
G / R three-color separation filter (R: 600-700 nm,
A bandpass filter of G: 500 to 590 nm and B: 400 to 490 nm was used. ) And exposed at 1/10 ″ at 2500 lux. Dampening water was supplied to the exposed emulsion surface of the light-sensitive material by a wire bar, and then superposed so that the image receiving material 201 and the film surface were in contact with each other. Was heated at 78 ° C., 83 ° C., 88 ° C. for 30 seconds, the image receiving material was peeled off from the light-sensitive material, and an image was obtained on the image receiving material, which image was obtained using a reflection densitometer X-Rite310 with a filter StatusA. The reflection density was measured: fog at the developing temperature of 83 ° C. of each light-sensitive material, and 78 ° C.
The relative sensitivities at 83 ° C. and 88 ° C. are shown in Table 11. The relative sensitivities of yellow, magenta, and cyan were examined by the logarithm of the reciprocal of the exposure amount that gives a density of 2.0, and the sensitivity at the developing temperature of 83 ° C. of the photosensitive material 104 was determined as 100.

[0153]

[Table 11]

From these results, the light-sensitive material of the present invention succeeded in suppressing fog in each layer and suppressing the sensitivity fluctuation when the developing temperature was changed. Further, the light-sensitive material and the image-receiving material of the present invention were processed into a roll type and set on Fujis Pictrostat 200 which was released in Japan from Fuji Film in December 1992. Further, the negative treated with Fuji Color Super HG400 was set in the slide enlarging unit. Development time is 83
Water application conditions / transport conditions, except that the temperature was set to 28 seconds
Fujispictrostat 200, including exposure control
The treatment was carried out under the standard conditions. Printed images from the negatives were obtained with all of the light-sensitive materials. Particularly, the light-sensitive materials 107 and 110 of the present invention were excellent in white background and maximum density, and images with further excellent image quality were obtained. Further, excellent images were obtained with the photographic material of the present invention even with negatives such as HG100 other than Fujicolor Super HG400 and Super Gold 100/200/400 manufactured by Eastman Kodak Company.

Example 2 How to Make a Photosensitive Silver Halide Emulsion

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Sensitive Layer)] In a well-stirred aqueous solution having the composition shown in Table 12, solutions (I) and (II) having the compositions shown in Table 13 were used. ) Solution was added simultaneously over 13 minutes, and 10 minutes after that, (II of the composition shown in Table 13 was used.
Solution (I) and solution (IV) were added over 33 minutes.

[0157]

[Table 12]

[0158]

[Table 13]

[0159]

[Chemical 52]

13 minutes after the addition of the solution III was started, 150 cc of a 0.35% aqueous solution of the sensitizing dye (a) was added over 27 minutes.

[0161]

[Chemical 53]

After washing with water and desalting (the 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 14. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0163]

[Chemical 54]

[0164]

[Table 14]

[0165]

[Chemical 55]

[0166]

[Chemical 56]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 16 were added to an aqueous solution having the composition shown in Table 15 and being well stirred. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 16 were added over 24 minutes.

[0168]

[Table 15]

[0169]

[Table 16]

After rinsing with water and desalting (pH was set to 3.9 using the precipitating agent b) by a conventional method, calcified 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, use the chemicals shown in Table 17 at 70 ° C.
I chemically sensitized. At the end of the chemical sensitization, a sensitizing dye,
Was added as a methanol solution (solution having the composition shown in Table 18). After chemical sensitization, the temperature was lowered to 40 ° C., 200 g of a gelatin dispersion of a stabilizer described later was added, and the mixture was stirred well and then stored. The yield of the obtained emulsion was 938 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0171]

[Table 17]

[0172]

[Chemical 57]

[0173]

[Table 18]

[0174]

[Chemical 58]

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Solution (I) and (II) having the compositions shown in Table 20 were added to an aqueous solution having the composition shown in Table 19 and being well stirred. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 20 were added over 24 minutes.

[0176]

[Table 19]

[0177]

[Table 20]

After washing with water and desalting (the precipitation agent a was used at a pH of 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 shown in Table 21. 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.

[0179]

[Table 21]

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 22, the solution having the composition shown in Table 23 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 612g.
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0182]

[Table 22]

[0183]

[Table 23]

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 24. 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.
Furthermore, 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) was repeatedly diluted with water and concentrated to reduce the amount of ethyl acetate to 17.6 times the amount of ethyl acetate in Table 24.

[0186]

[Table 24]

A gelatin dispersion of reducing agent was prepared according to the recipe in Table 25. 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.
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.

[0188]

[Table 25]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 26. 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 10,000 r
dispersed at pm. Water was added to this and stirred to obtain a uniform dispersion.

[0190]

[Table 26]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 27. That is, each component was mixed and dissolved, and then dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.2
The one having a thickness of 5 μm was used. )

[0192]

[Table 27]

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.

[0194]

[Chemical 59]

[0195]

[Chemical 60]

[0196]

[Chemical formula 61]

[0197]

[Chemical formula 62]

[0198]

[Chemical formula 63]

[0199]

[Chemical 64]

[0200]

[Chemical 65]

[0201]

[Chemical formula 66]

[0202]

[Chemical formula 67]

[0203]

[Chemical 68]

[0204]

[Chemical 69]

A photothermographic material 101 shown in Table 28 was prepared using the above materials.

[0206]

[Table 28]

[0207]

[Table 29]

[0208]

[Chemical 70]

[0209]

[Chemical 71]

[0210]

[Chemical 72]

[0211]

[Chemical formula 73]

[0212]

[Chemical 74]

A method for forming the photosensitive material 102 will be described. When making a dispersion of a magenta dye-donor compound,
The compound (III-d-5) was added to the dye-donating compound at the same time as 6.
A dispersion was made in the same manner except that 6 g was added. When making a dispersion of a cyan dye-donor compound,
A dispersion of a cyan dye-donor compound was prepared in the same manner except that 6.5 g of (III-d-5) was added. Except for these, the same material as the photosensitive material 101 was used. Similarly, the light-sensitive materials 103 to 110 shown in Table 30 were prepared. The compounds shown in Table 30 such as the compounds of the present invention were added in the amounts corresponding to the coating amounts shown in Table 30 when preparing dispersions of each dye-donor compound.

[0214]

[Table 30]

These light-sensitive materials 101 to 110 were manufactured by Fuji Photo Film Co., Ltd. using a digital color printer FUJIX PICTOROGRAPHY PG-3000, using PG-SG for PG-3000 as a dye fixing material at a developing temperature of 75 ° C. Exposure and processing were performed under standard conditions except that the temperature was set to 80 ° C and 85 ° C. (The conditions of exposure and processing are shown in Table 31.) However, the exposure was 2.5 on the light-sensitive material.
The emission time of the laser was modulated so that the exposure amount was 1/10 for each cm, and the characteristic curve of the light-sensitive material was obtained.

[0216]

[Table 31]

The image is taken as a reflection density measuring instrument X-Rite310.
Was used to measure the reflection density with the filter StatusA. Fog at developing temperature of 80 ° C for each light-sensitive material, and 75
Table 32 shows the relative sensitivities at 80 ° C, 85 ° C, and 80 ° C. The relative sensitivities of yellow, magenta, and cyan were examined by the logarithm of the reciprocal of the exposure amount that gives a density of 2.0, and the sensitivity at the developing temperature of 80 ° C. of the photosensitive material 104 was determined as 100.

[0218]

[Table 32]

From these results, it can be seen that the light-sensitive material of the present invention is a light-sensitive material in which fogging is suppressed in each layer and sensitivity fluctuations are small when the developing temperature is changed.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 9, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0111

[Correction method] Change

[Correction content]

[0111]

[Chemical 29]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Correction content]

[0115]

[Chemical 30]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0132

[Correction method] Change

[Correction content]

[0132]

[Table 4]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Correction content]

[0133]

[Table 5]

Claims (2)

[Claims] 1. A photosensitive silver halide, at least one compound represented by the general formula (I) or (II), a binder, and a diffusible dye corresponding to silver development or vice versa on a support. A heat-developable color light-sensitive material having a dye-donating compound that releases light and / or a reducing agent, further comprising at least one compound represented by the general formulas (III-a) to (III-g). A heat-developable color photosensitive material. [Chemical 1] [In the general formulas (I) and (II), Ball represents an organic ballast group capable of making the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ba
11 may not be necessary. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ₁ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. R ₂ is a hydrogen atom, a halogen atom, a substituted or unsubstituted cycloalkyl group, an aralkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acylamino group, alkylthio group, or arylthio group Represents n represents an integer of 0 to 5, and when n is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring. When Y represents an atomic group necessary for completing the naphthalene nucleus, Ball and R
₂ can be attached to any of the ring systems so formed. ] [Chemical 2] In formulas (III-a) to (III-g), A represents a divalent electron-withdrawing group, R ₁ represents an alkyl group, an aryl group,
Alkoxy group, aryloxy group, alkylamino group,
Represents an anilino group and a heterocyclic group. p is an integer of 1 or 2. R ₂ represents an alkyl group, an alkoxy group, a hydroxyl group or halogen, and m is an integer of 0 to 4. Q represents a benzene ring or a hetero ring which may be condensed with the phenol ring. R ₃ represents an alkyl group, an aryl group or a heterocyclic group. Y ₁ is an aryl group, an alkyl group, a heterocyclic group, a —P (O) (Rb) —Ra group, or —
Represents a C (O) -Ra group. R _'4 represents an alkylene group, arylene group or aralkylene group,, R ₄ represents an alkyl group or an aryl group. However, Y ₁ and R ₄ are not an alkyl group at the same time. Ra, R
b represents an alkyl group, an aryl group, an amino group, an alkoxy group or an aryloxy group. n represents an integer of 1 to 5. R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a phenylsulfonyl group, or an acyl group.
R ₆ represents the same substituent as R ₄ . R ₅ and R ₆ may be ring-closed to form a 5- to 7-membered ring. R ₇ and R ₈ are R
_It represents the same substituent as ₄ , but may be closed to form a 5- to 7-membered ring. [Chemical 3] Represents a 5- to 7-membered heterocycle. 2. A heat-developable color light-sensitive material according to claim 1, which contains at least one compound represented by formula (III) together with the dye-donating compound.