JPH04255845A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a positive picture with high maximum image density by dispersing a specified compd. as well as a reducible compd. capable of supplying a dye in a binder as the same emulsion and including the binder in a photosensitive layer including a photosensitive silver halide. CONSTITUTION:A compd. represented by the formula as well as a reducible compd. capable of supplying a dye is dispersed in a binder as the same emulsion and the binder is included in at least one photosensitive layer including a photosensitive silver halide. In the formula, L is a simple bonding or divalent coupling group, and (n) is an integer of 1 to 4, and R1 is a hydrogen atom, carboxyl group, alkyl group, aralkyl group, etc., when n=1, and R1 is a divalent to quadrivalent residue when n=2, 3 or 4. And R2 is a hydrogen atom, carboxyl group, alkyl group, aryloxycarbonyl group, alkoxycarbonyl group, etc., and the individual combinations of L and R2 may be the same or different when (n) is 2, 3 or 4.

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 photosensitive material, which is suitable for mass production and capable of producing positive images with high maximum density.

0002

[Prior Art] Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, for example, see page 242 of ``Fundamentals of Photographic Engineering,'' Non-Silver Salt Photography Edition (published by Corona Publishing, 1982). ~255 pages, U.S. Patent No. 4500
It is described in No. 626, etc.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DDR compound in an oxidized form without dye-releasing ability is made to coexist with a reducing agent or its precursor, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development. A method has been proposed in which a diffusible dye is released by reducing it with a reducing agent that remains unoxidized. In addition, European Patent Publication No. 220746 and Publication of Technical Report No. 87-6199 (Vol. 12, No. 22) describe compounds that release diffusible dyes by a similar mechanism, including N-X bonds (X is an oxygen atom, a nitrogen atom, or A heat-developable color photosensitive material using a non-diffusible compound that releases a diffusible dye upon reductive cleavage of a sulfur atom (representing a sulfur atom) has been described.

[0004] In the positive image forming method using the above-mentioned reducible dye-donating compound, an electron donor and an electron transfer agent are usually used in combination as reducing agents.

However, in the image forming method in which thermal development is performed using a combination of an electron donor and an electron transfer agent, the ability to reduce silver ions to silver is high, and this reduction reaction occurs even in unexposed areas. There was a problem that the maximum density of a positive image decreased.

For this reason, as a heat-developable photosensitive material that gives a positive image with a high maximum density, JP-A-1-222
No. 256 discloses a method using a mercapto compound or an acetylene compound, and JP-A-2-34735 discloses a method using a mercapto compound and an acetylene compound in specific layers.

However, when these heat-developable photosensitive materials are manufactured in large quantities, it is necessary to use a coating solution that has been kept warm after preparation, rather than one that has just been prepared. Heat-developable photosensitive materials manufactured using coating liquids have a problem in that the maximum density decreases.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable color photosensitive material that can be mass-produced and provides a positive image with a high maximum density even when manufactured using a coating solution that has been kept warm. It is about providing.

[0009]

[Means for Solving the Problems] Such an object is achieved by the configuration (1) below.

(1) A heat-developable color photosensitive material having on a support at least a photosensitive silver halide, a binder, an electron transfer agent, an electron donor, and a reducible dye-donating compound that releases a diffusible dye upon reduction. The material is characterized in that at least one photosensitive layer containing the photosensitive silver halide contains the compound of formula 2 dispersed in the binder as the same emulsion together with the reducible dye-providing compound. A heat-developable color photosensitive material.

[0011]

[Case 2]

[In formula 2, L is a simple bond or
Represents a divalent linking group. n represents an integer from 1 to 4. n=
When 1, R1 is a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,
Represents an aralkyl group, an aryl group or a heterocyclic group. n
= 2, 3 or 4, R1 is divalent, trivalent or 4
Represents a residue of valence. R2 represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl group, a heterocyclic group, or a carbamoyl group. When n is 2, 3 or 4, each combination of L and R2 may be the same or different. However, this excludes the case where L is a simple bond and when n=1, both R1 and R2 are hydrogen atoms. ]

[0013]

[Operation] According to the present invention, the compound of formula 2 is dispersed in a binder as the same emulsion in at least one photosensitive layer together with a reducible dye-providing compound that releases a diffusible dye when reduced. Since it is contained, even in heat-developable color photosensitive materials produced by keeping the coating solution warm and aging, a positive image with a high maximum density can be obtained. Therefore, even in the case of mass production, the photographic performance remains constant and is suitable for mass production.

[0014]

[Specific Configuration] The specific configuration of the present invention will be explained in detail below.

The heat-developable color photosensitive material of the present invention has a reducible dye-donating property in which a compound of formula 2 is added to at least one photosensitive layer containing photosensitive silver halide to release a diffusible dye upon reduction. It is dispersed and contained in a binder together with other compounds in the same emulsion.

In formula 2, L is a simple bond or 2
Represents a valence linking group. n represents an integer from 1 to 4. n=1
When R1 represents a hydrogen atom, a carboxyl group, or a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, or heterocyclic group, and n=2, 3, or 4
When R1 represents a divalent, trivalent or tetravalent residue, respectively. R2 is a hydrogen atom, a carboxyl group, or a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryloxycarbonyl group, alkoxycarbonyl group, aryl group, heterocyclic group, or carbamoyl group. represent. n is 2
, 3 or 4, each combination of L and R2 may be the same or different. However, this excludes the case where L is a simple bond and when n=1, both R1 and R2 are hydrogen atoms.

First, the compound of formula 2 will be explained in detail.

The alkyl groups of R1 and R2 may be linear or branched, and examples of the alkyl groups include butyl, isobutyl, hexyl, heptyl, octyl, dodecyl, pentadecyl, etc. Examples of substituents for substituted alkyl groups include alkoxy groups (for example, methoxy groups, etc.), aryloxy groups, acyloxy groups, heterocyclic oxy groups, hydroxy groups, carboxyl groups or salts thereof, formyl groups, acyl groups, Substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, sulfino group or its salt, sulfo group or its salt, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, Substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, nitro group, nitroso group, cyano group, halogen atom, alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group, substituted or unsubstituted amino group, cycloalkyl group , an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkynyl group (for example, an ethynyl group), and the like. There may be two or more of these substituents.

Examples of cycloalkyl groups for R1 and R2 include cyclopentyl group, cyclohexyl group, decahydronaphthyl group; examples of alkenyl groups include propenyl group, isopropenyl group, styryl group, etc.; examples of alkynyl groups include is an ethynyl group, phenylethynyl group, etc.:
Examples of the aralkyl group include benzyl group and phenethyl group. These groups may have the substituents described for the alkyl groups. Also, the substituents are 2
There may be more than one.

[0020] Examples of the aryl group for R1 and R2 include phenyl group, naphthyl group, etc., and examples of substituents for substituted aryl group include alkyl group (methyl group, dodecyl group, etc.), alkenyl group, aryl group, etc. group, cycloalkyl group, aralkyl group, alkynyl group, cyano group, nitro group, nitroso group, substituted or unsubstituted amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoyl group Amino group, hydroxyl group, alkoxy group, aryloxy group,
Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclicoxy group, acyloxy group, heterocyclic group (5-6
Member rings, especially nitrogen-containing heterocycles are preferred. ), alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, mercapto group, formyl group,
Acyl group, alkylsulfonyl group, arylsulfonyl group, carboxylic acid group or its salt, sulfonic acid group or its salt, sulfino group or its salt, halogen atom (fluorine, bromine, chlorine, iodine), substituted or unsubstituted, ureido group, carbamoyl group, sulfamoyl group, etc. These substituents may be further substituted. Furthermore, there may be two or more substituents as exemplified above.

The heterocyclic group for R1 and R2 is preferably a 5- or 6-membered group, such as furyl, thienyl, benzothienyl, pyridyl, and quinolyl. These heterocyclic groups may have the same substituents as the above substituted aryl group.

Examples of the aryloxycarbonyl group for R2 include a phenoxycarbonyl group; examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The carbamoyl group of R2 is -CON
In addition to H2, the above substituted or unsubstituted alkyl group,
Examples include an aryl group and a carbamoyl group substituted with a heterocyclic group.

[0024] When n is 2, 3 or 4, R1 represents a divalent, trivalent or tetravalent residue, for example, each hydrogen atom is removed from the monovalent group of R1 or R2 described above. Examples include groups with one, two or three removed. Also, -NH- is included in R1 when n=2.

L represents a simple bond or a divalent linking group (preferably -O-CO- group or -CONH- group).

[0026] n is preferably 1 or 2.

Among these, compounds in which either R1 or R2 is a hydrogen atom and the other is a group other than a hydrogen atom are preferred.

More preferably, either R1 or R2 is a hydrogen atom and the other is a phenyl group or a substituted phenyl group. In particular, a compound of formula 3 is preferred.

[0029]

[Chemical formula 3]

In formula 3, m is 1 or 2. R
3 represents an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, or heterocyclic group having 1 to 20 carbon atoms when m=1;
2 represents an alkylene group, an arylene group, or a cycloalkylene group. Moreover, these substituents may be further substituted with other substituents.

[0031] R3 will be explained in detail below.

In the case of an alkyl group, it may be linear or branched, and examples of the alkyl group include propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, heptyl group. group, isoheptyl group, octyl group, nonyl group, decyl group, dodecyl group, and pentadecyl group. Examples of substituents for substituted alkyl groups include cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, heterocyclic groups, halogen atoms (fluorine, chlorine, bromine, iodine), hydroxyl groups, alkoxy groups, and aryl groups. Oxy group, acyloxy group, heterocyclic oxy group, carboxyl group or its salt, formyl group,
Acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, mercapto group, alkylthio group, arylthio group, sulfino group or its salt, sulfo group or its salt, alkylsulfinyl group, arylsulfinyl group group, alkylsulfonyl group, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group , an aryloxycarbonylalkylsulfonylamino group, an arylsulfonylamino group, a substituted or unsubstituted sulfamoylamino group, a nitro group, a nitroso group, and the like. Two or more of these groups may be present, and the substituents may be further substituted.

Examples of cycloalkyl groups include cyclopentyl, cyclohexyl and decahydronaphthyl groups; examples of alkenyl groups include propenyl, isopropenyl and styryl groups. These groups may have the substituents described for the alkyl groups. Moreover, there may be two or more substituents.

Examples of aryl groups include phenyl groups, naphthyl groups, etc. Examples of substituents for substituted aryl groups include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, Heterocyclic group (5- to 6-membered ring, preferably nitrogen-containing heterocycle),
Halogen atoms (fluorine, chlorine, bromine, iodine), hydroxyl groups, alkoxy groups, aryloxy groups, acyloxy groups,
Heterocyclic oxy group, carboxyl group or salt thereof, formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, mercapto group, alkylthio group, arylthio group, sulfino group or their salt, sulfo group or its salt, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group,
Substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group, nitro group, nitroso group, etc. These substituents may be further substituted. Furthermore, there may be two or more substituents as exemplified above.

Examples of aralkyl groups include benzyl and phenethyl groups. These substituents may have one or more of the substituents described for the alkyl group or aryl group, and these substituents may be further substituted.

The heterocyclic group is preferably 5- or 6-membered, such as furyl, thienyl, benzothienyl, pyridyl, and quinoline. These heterocyclic groups may have the same substituents as the above substituted aryl group.

Examples of alkylene groups include methylene group, ethylene group, trimethylene group, propylene group, etc.; examples of arylene groups include (o-, m-, p-) phenylene group, (1,4-, etc.) Examples of cycloalkylene groups include naphthylene groups and the like; examples of cycloalkylene groups include cyclohexylene groups. The above divalent residue may have one or more substituents as explained for the alkyl group or aryl group, and the substituent may be further substituted.

Among these, R3 is preferably an alkyl group or a cycloalkyl group having 3 or more carbon atoms. More preferably, R3 is an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group.

Further, m is particularly preferably 1.

Specific examples of the compound of formula 2 in the present invention are shown below.

[0041]

[C4]

[0042]

[C5]

[0043]

[C6]

[0044]

[Chemical 7]

[0045]

[Chemical formula 8]

[0046]

[Chemical formula 9]

The acetylene compound of chemical formula 2 of the present invention is represented by chemical formula 1
As shown in 0, it is easily obtained from the condensation reaction of 4-ethynylaniline and an acid chloride of a carboxylic acid.

[0048]

[Chemical formula 10]

4-ethynylaniline in chemical formula 10 is HELVETICA CHIMICA ACTA
It can be synthesized by the method described in Vol. 54, p. 2066 (1971).

The content of the acetylene compound of formula 2 is preferably 10 -4 mol to 1 mol, particularly 10 -3 mol to 5×10 -1 mol per m 2 of the additive layer.

Next, the reducible dye-providing compound used in the present invention will be explained.

The reducible dye-providing compound used in the present invention is preferably a compound represented by the following formula [C-1]. Formula [C-I] PWR-(Time)t-Dye In the formula, PWR is reduced to -(Time)
Represents a group that releases t-Dye.

Time is -(Time)t from PWR
- D through the subsequent reaction after being released as Dye
Represents a group that releases ye. t represents an integer of 0 or 1. Dye represents a dye or its precursor.

First, PWR will be explained in detail.

[0055] PWR is disclosed in US Pat. No. 4,139,389, or US Pat. No. 4,139,379, US Pat.
No., JP-A-59-185333, JP-A No. 57-84453
Even if it corresponds to a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. Good, US Patent No. 4232107
As disclosed in JP-A No. 59-101649, Research Disclosure (1984) IV, 24025, or JP-A No. 61-88257, after being reduced, the photographic reagent is released into the molecule by an electron transfer reaction. It may correspond to the moiety containing the electron-accepting quinonoid center in the compound to be released and the carbon atom that connects it to the photographic reagent. Also, JP-A-56-142
No. 530, U.S. Pat. No. 4,343,893, U.S. Pat. No. 46,198
The aryl group substituted with an electron-withdrawing group in the compound whose single bond is cleaved to release the photographic reagent after reduction as disclosed in No. 84 and the atom connecting it to the photographic reagent (sulfur or carbon atom or nitrogen It may also correspond to a part containing (atom). Also, U.S. Patent No. 44502
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom connecting it to a photographic reagent as disclosed in U.S. Pat. It may correspond to the dieminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in No. 4,609,610.

[0056]More preferable ones include European Patent No. 220746A2, Published Technical Report No. 87-6199, US Pat.
No. 63-201654, etc., N in one molecule.
-X bond (X represents oxygen, sulfur or nitrogen atom)
and a compound having an electron-withdrawing group, patent application No. 1068/1986
Compound having SO2 -X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 85, JP-A-63-2
71344, a PO-X bond (X
is the same meaning as above) and an electron-withdrawing group, a C-X' bond (X' is the same as X or represents -SO2-) in one molecule as described in JP-A No. 63-271341. ) and a compound having an electron-withdrawing group. Also,
Compounds described in Japanese Patent Applications No. 62-319989 and No. 62-320771 that release a diffusible dye by cleavage of a single bond by a π bond conjugated with an electron-accepting group after reduction can also be used.

In order to more fully achieve the object of the present invention, among the compounds of formula [C-I], those represented by formula 11 are preferred.

[0058]

[Chemical formula 11]

In chemical formula 11, (Time)t -Dy
e binds to at least one of R101, R102, or EAG.

The portion corresponding to the PWR in Formula 11 will be explained.

X is an oxygen atom (-O-), a sulfur atom (-S
-) represents a group containing a nitrogen atom (-N(R103)-).

R101, R102 and R103
represents a group other than a hydrogen atom or a simple bond.

R101, R102 and R103
Groups other than hydrogen atoms represented by include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups,
Examples include a heterocyclic group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, and these groups may have a substituent.

R101 and R103 are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups,
Aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc. are preferred. The number of carbon atoms in R101 and R103 is 1
~40 is preferred.

R102 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples include R101,
This is the same as the acyl group and sulfonyl group mentioned for R103. The number of carbon atoms is preferably 1 to 40.

R101, R102 and R103
may be combined with each other to form a five- to eight-membered ring.

[0067] As X, oxygen is particularly preferred.

[0068] EAG will be described later.

Furthermore, in order to achieve the object of the present invention, among the compounds of formula 11, the compound of formula 12 is preferable.

[0070]

[Chemical formula 12]

(Time) t-Dye is R104,
Binds to at least one of the EAGs. X has the same meaning as above.

R104 represents an atomic group that is bonded to X or a nitrogen atom to form a five- to eight-membered monocyclic or condensed heterocycle including the nitrogen atom.

EAG represents a group that accepts electrons from a reducing substance and is bonded to a nitrogen atom. Chemical 1 as EAG
Group No. 3 is preferred.

[0074]

[Chemical formula 13]

In Chemical Formula 13, Z1 is as shown in Chemical Formula 14.

[0076]

[Chemical formula 14]

Vn represents an atomic group forming a 3- to 8-membered aromatic group together with Z1 and Z2, and n is 3 to 8.
represents an integer.

V3;-Z3-, V4;-Z3-
Z4 −, V5; −Z3 −Z4−Z5 −, V6
;-Z3 -Z4 -Z5 -Z6 -, V7 ;-Z
3 -Z4 -Z5 -Z6 -Z7 -, V8 ;-
Z3 -Z4 -Z5 -Z6 -Z7 -Z8 -. Z2 to Z8 are each shown in Chemical Formula 15.

[0079]

[Chemical formula 15]

Sub in Z1 to Z8 each represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Sub may be the same or different, or may be bonded to each other to form a three- to eight-membered saturated or unsaturated carbocyclic or heterocyclic ring.

In the group shown in Formula 13, the sum of the Hammett substituent constant sigma para of the substituents is +0.50 or more, more preferably +0.70 or more, and most preferably +0.8.
Select Sub so that it is 5 or more.

EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire chemical compound. Examples of the physical properties of the entire compound include the ability to adjust the ease with which it accepts electrons, as well as water solubility,
It can be used to adjust oil solubility, diffusibility, sublimability, melting point, dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with electrophilic groups, etc.

[0083] A specific example of EAG is European Patent Publication 220
No. 746A2, pages 6-7.

Time represents a group that releases Dye through a subsequent reaction triggered by cleavage of a nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bond.

Various groups represented by Time are known, for example, as described in JP-A-61-147244, pages (5) to (6).
Examples include groups described in Japanese Patent Application No. 61-236549, pages (8) to (14), and Japanese Patent Application No. 61-88625, pages (36) to (44).

Dyes represented by dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl groups, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. It should be noted that these dyes can also be used in a temporarily shortened form that can restore the color during development.

Specifically, EP76492A, Japanese Unexamined Patent Publication No. 5
Dye disclosed in No. 9-165054 can be used.

The compound represented by Formula 11 or Formula 12 must itself be non-migratory in the photographic layer, and for this purpose, a carbon at the EAG, R101, R102, R104 or X position (particularly at the EAG position) is required. It is desirable to have 8 or more ballast groups.

Typical specific examples of the reducible dye-providing compound used in the present invention are listed in Chemical Formulas 16 to 23, but the present invention is not limited thereto.
Dye-donating compounds described in No. 0746A2, Kokai Technical Report No. 87-6199, etc. can also be used.

[0090]

[Chemical formula 16]

[0091]

[Chemical formula 17]

[0092]

[Chemical formula 18]

[0093]

[Chemical formula 19]

[0094]

[C20]

[0095]

[C21]

[0096]

[C22]

[0097]

[C23]

These compounds can be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-providing compound to be used depends on the extinction coefficient of the dye, but is in the range of 0.05 to 5 mmol/m2, preferably 0.1 to 3 mmol/m2. The dye-providing compounds can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues, for example, at least one cyan, magenta, and yellow dye-providing compound may be added to a layer containing silver halide, as described in JP-A-60-162251. Alternatively, it is also possible to use a mixture of two or more dye-providing compounds that release mobile dyes (diffusible dyes) having different hues, such as by mixing and containing them in adjacent layers.

The acetylene compound and the dye-providing compound of the present invention shown in formula 2 are used as the same emulsion, dispersed in a hydrophilic colloid as a binder. At this time, it is preferable to use all of the compound of the present invention represented by Chemical Formula 2 and the dye-providing compound used in the same photosensitive layer as the same emulsion. It can also be used as a thing. When used as a part of the emulsion, it is preferable that all the compounds of the present invention and a part of the dye-providing compound used in a large amount (by weight) be in the same emulsion. The ratio of the amount of the dye-providing compound to the compound of the present invention [dye-donating compound/compound of the present invention] is 1/1 by weight.
-500/1, preferably 5/1 - 100/1.

In the present invention, in order to introduce these into the photosensitive layer which is a hydrophilic colloid layer, a high boiling point organic solvent such as phthalic acid alkyl ester (dibutyl phthalate,
dioctyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic esters ( (e.g., octyl benzoate), alkylamides (e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g., tributyl trimesate), described in Japanese Patent Application No. 61-231500 carboxylic acids, JP-A-59-83154, JP-A-59-83154
-178451, 59-178452, 59-
No. 178453, No. 59-178454, No. 59-1
No. 78455, No. 59-178457 using the method described in U.S. Pat.
For example, a method in which the solution is dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., and then dispersed in a hydrophilic colloid. Use. Further, the above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like as required. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing compound used. Further, the amount is 5 g or less, preferably 2 g or less per 1 g of a diffusion-resistant reducing agent that is often placed in the same layer as a dye-donating compound. Furthermore, 1 g or less of high boiling point organic solvent per 1 g of binder, preferably 0.5 g
Below, more preferably below 0.3g is appropriate. Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-599
The polymer dispersion method described in No. 43 can also be used. In addition, it can be directly dispersed in an emulsion, or it can be dissolved in water or alcohol and then dispersed in gelatin or an emulsion.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the binder in the form of fine particles in addition to the method described above (for example, JP-A-59-174830,
53-102733, Japanese Patent Application No. 62-106882, etc.).

[0103] In the above, when dispersing a hydrophobic substance into a hydrophilic colloid, various surfactants can be used.
Those listed as surfactants on pages 1 to 38 can be used.

In the present invention, an electron donor and an electron transfer agent (
ETA), but details of these compounds can be found in European Patent Publication No. 220746A2 and Technical Report No. 87-61.
It is described in No. 99, etc. Particularly preferred electron donors (
or its precursor) is a compound represented by chemical formula 24 or chemical formula 25.

[0105]

[C24]

[0106]

[C25]

In Chemical Formulas 24 and 25, A101 and A102 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, as the nucleophile, OH-, R
Anionic reagents such as O-(R; alkyl group, aryl group, etc.), hydroxamic acid anions, SO32-, and non-ionic reagents such as primary or secondary amines, hydrazine, hydroxylamines, alcohols, and thiols. Examples include compounds with a shared electron pair.

Preferred examples of A101 and A102 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a diarylphosphoryl group, or JP-A-59-197037
No. 59-20105, and A101 and A102 may be R201 , R202 , R203 and R204 when possible.
may be combined with each other to form a ring. Also A101
, A102 may be the same or different.

R201, R202, R203 and R204 each represent a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a heterocyclic thio group,
It represents a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, an imide group, a carboxyl group, a sulfonamide group, etc. These groups may have a substituent if possible.

[0111] However, the total number of carbon atoms in R202 to R204 is 8 or more. Moreover, in chemical formula 24, R20
2 and R202 and/or R203 and R204
However, in chemical formula 25, R201, R202, R2
02 and R203 and/or R203 and R20
4 may combine with each other to form a saturated or unsaturated ring.

Among the electron donors represented by Formula 24 or Formula 25, those in which at least two of R201 to R204 are substituents other than hydrogen atoms are preferred. Particularly preferred compounds are those in which at least one of R201 and R202 and at least one of R203 and R204 are substituents other than hydrogen atoms.

[0113] A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination.

Specific examples of electron donors are listed below, but the present invention is not limited to these compounds.

[0115]

[C26]

[0116]

[C27]

[0117]

[C28]

[0118]

[C29]

[0119]

[C30]

The amount of the electron donor (or its precursor) to be used has a wide range, but is preferably from 0.01 mol to 50 mol, particularly from 0.1 mol to 50 mol, per mol of positive dye-donating compound.
A preferred range is on the order of 5 moles. Also, 0.001 mol to 5 mol, preferably 0.001 mol to 1 mol of silver halide.
01 mole to 1.5 mole.

E used in combination with these electron donors
As TA, any compound can be used as long as it is oxidized by silver halide and the oxidized form thereof has the ability to cross-oxidize the electron donor, but a mobile compound is preferable.

Particularly preferable ETA is chemical formula 31 or chemical formula 3
This is the compound No. 2.

[0123]

[Chemical formula 31]

[0124]

[C32]

In formulas 31 and 32, R represents an aryl group. R301 , R302 , R303 , R3
04, R305 and R306 represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group or an aryl group, and may be substituted if possible. Further, these may be the same or different.

In the present invention, the compound of formula 32 is particularly preferred. In chemical formula 32, R301, R302,
R303 and R304 are each preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group,
More preferably, it is a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group, or a phenyl group substituted with a hydrophilic group such as a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group.

Specific examples of ETA are shown in Chemical Formulas 33 to 35.

[0128]

[Chemical formula 33]

[0129]

[C34]

[0130]

[C35]

[0131] The ETA precursor used in the present invention does not have a developing effect during storage of the photosensitive material before use, but
It is a compound that can release ETA only by the action of a suitable activator (eg, base, nucleophile, etc.) or heating.

In particular, the ETA precursor used in the present invention is E
Because the reactive functional group of TA is blocked with a blocking group, it does not function as an ETA before development, but it functions as an ETA because the blocking group is cleaved under alkaline conditions or when heated. Can be done.

As the ETA precursor used in the present invention, for example, 1-phenyl-3-pyrazolidinone 2 and 3
- Acyl derivatives, 2-aminoalkyl or hydroxyalkyl derivatives, hydroquinone, metal salts of catechol (lead, cadmium, calcium, barium, etc.), halogenated acyl derivatives of hydroquinone, oxazine and bisoxazine derivatives of hydroquinone, lactone-type ETA precursors In addition to hydroquinone precursors with quaternary ammonium groups, cyclohexakis-2-ene-1,4-dione type compounds, compounds that release ETA through electron transfer reactions, and compounds that release ETA through intramolecular nucleophilic substitution reactions. Examples include compounds that block phthalide groups, ETA precursors blocked with indomethyl groups, and the like.

[0134] The ETA precursor used in the present invention is a known compound, for example, US Pat.
No. 241967, No. 3246988, No. 329597
No. 8, No. 3462266, No. 3586506, No. 3
No. 615439, No. 3650749, No. 420958
No. 0, No. 4330617, No. 4310612, British Patent No. 1023701, No. 1231830, No. 12
No. 58924, No. 1346920, JP-A-57-40
No. 245, No. 58-1139, No. 58-1140,
Developer precursors described in Japanese Patent Nos. 59-178458, 59-182449, and 59-182450 can be used.

[0135] In particular, JP-A-59-178458, JP-A No. 59-178458;
The precursors of 1-phenyl-3-pyrazolidinones described in No. 182449 and No. 59-182450 are preferred.

[0136] ETA and an ETA precursor can also be used in combination.

In the present invention, the combination of electron donor and ETA is preferably incorporated into the heat-developable color photosensitive material. Electron donors, ETAs, or their precursors can be used in combination of two or more, and can be used in emulsion layers (blue-sensitive layers, green-sensitive layers, red-sensitive layers, infrared-sensitive layers, ultraviolet-sensitive layers, etc.) in light-sensitive materials.
It can be added to each emulsion layer, only to some emulsion layers, to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, protective layer, etc.), or even to all emulsion layers. It can also be added to the layer. The electron donor and ETA can be added to the same layer or to separate layers. Additionally, these reducing agents can be added in the same layer as the dye-donating compound or in separate layers; however, the diffusion-resistant electron donor is present in the same layer as the dye-donating compound. is preferred. ETA can be incorporated into the image-receiving material (dye fixing layer), or if a small amount of water is present during thermal development, it can be dissolved in this water. The preferred amount of the electron donor, ETA or their precursor used is 0.01 to 50 mol in total, preferably 0.1 to 5 mol, per 1 mol of the dye-donating compound, and 0.1 to 5 mol, preferably 0.1 to 5 mol, per mol of silver halide. 0.001 to 5 mol in total, preferably 0.01 to 5 mol
It is 1.5 mol.

[0138] Furthermore, ETA accounts for 60 mol% or less, preferably 40 mol% or less of the total reducing agent. When ETA is dissolved in water and supplied, the concentration of ETA is 10-4 mol/
1 to 1 mol/l is preferred.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound on a support, and further includes: An organometallic salt oxidizing agent or the like can be contained as necessary. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

[0140] In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination. . For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials. Further, each of these photosensitive layers may be divided into two or more layers as necessary.

[0141] The heat-developable photosensitive material includes a protective layer, an undercoat layer,
Various auxiliary layers such as an intermediate layer, a yellow filter layer, an antihalation layer, and a backing layer can be provided.

The silver halide that can be used in the present invention 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 is a surface latent image type emulsion. A surface latent image type emulsion is an emulsion in which a latent image is mainly formed on the grain surface, and is also called a negative type emulsion. The definition of surface latent image type emulsion is given in Japanese Patent Publication No. 58-9410.
It is stated in the No.

The silver halide emulsion of the present invention 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. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. The particle size is preferably 0.1-2μ, particularly 0.2-1.5μ. The crystal habits of silver halide grains are cubic, octahedral, tetradecahedral,
It may be in the form of a plate with a high aspect ratio or in any other form.

[0145] Specifically, US Pat. No. 4,500,626, column 50, US Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

[0147] The coating amount of photosensitive silver halide used in the present invention is 1 mg to 10 g/m2 in terms of silver.
is within the range of

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

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include those described in US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids, and other compounds described in columns 52 and 53 of the present invention. Also, JP-A-60-113
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 235, and JP-A-61-24
Acetylene silver described in No. 9044 is also useful. Two or more types of organic silver salts may be used in combination.

The above organic silver salt is photosensitive silver halide 1
per mole, from 0.01 to 10 moles, preferably 0.01 to 10 moles.
01 to 1 mole can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m 2 in terms of silver.

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

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

[0153] Specifically, US Pat.
RD17029 (1978), pages 12-13.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, Patent No. 3615641, patent application 1986
1-226294 etc.).

These sensitizing dyes may be added to the emulsion during or before chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. No. 4,183,756 and US Pat. No. 4,225,666. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the light-sensitive material or the dye-fixing material. Examples include pages (26) to (2) of JP-A-62-253159.
Examples include those listed on page 8). Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and pullulan, and polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, super absorbent polymers described in JP-A No. 62-245260, etc.
That is, homopolymers of vinyl monomers having -COOM or -SO3 M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Sumikagel L-5H) manufactured by Kagaku Co., Ltd. is also used. Two or more of these binders can also be used in combination.

[0158] When employing a system in which heat development is performed by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to rapidly absorb water. Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to another material after transfer.

[0159] In the present invention, the amount of binder applied is 1
The amount per m2 is preferably 20 g or less, particularly 10 g or less, and more preferably 7 g or less.

[0160] The constituent layers (including the back layer) of the photosensitive material or dye-fixing material may contain additives for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A-62-245258, JP-A-62-136648, JP-A-62-110066, etc. can be used. especially,
Using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent the mordant layer from cracking, and using a polymer latex with a high glass transition point for the back layer can prevent curling. .

[0161] As described above, the dye-providing compound is introduced into the photosensitive layer as the same emulsion together with the compound of the present invention, but other dye-providing compounds and diffusion-resistant reducing agents to which this method is adopted can also be used. These hydrophobic additives can be introduced into the layers of the photosensitive material by known methods such as those described in US Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-open Nos. 59-83154 and 59-178
No. 451, No. 59-178452, No. 59-1784
No. 53, No. 59-178454, No. 59-17845
A high boiling point organic solvent as described in No. 5, No. 59-178457, etc. can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

[0162] The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-providing compound used.
It is as follows. In addition, for 1 g of diffusion-resistant reducing agent, 5
g or less, preferably 2 g or less. Furthermore, 1 cc or less, and even 0.5 cc per 1 g of binder.
Below, 0.3 cc or less is particularly suitable. Special Public Service 1977-
The dispersion method using a polymer described in No. 39853 and JP-A No. 51-59943 can also be used. In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, Nos. (37) to (38) of JP-A-59-157636
Those listed as surfactants on page 1 can be used.

[0164] In the present invention, a compound can be used in the light-sensitive material to activate the development and to stabilize the image at the same time. Specific compounds preferably used are described in columns 51-52 of US Pat. No. 4,500,626.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive 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 relationships described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

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.
A specific example is US Pat. No. 4,500,626 No. 58.
Column 59 and JP-A-61-88256 No. (32) to (4)
1), the mordant described in JP-A-62-244043,
Examples include those described in No. 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may also be used. The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

[0167] In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, JP-A No. 62-253159 (25
), No. 62-245253, etc.

Furthermore, various silicone oils (all silicone oils ranging from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used for the above purpose. As an example, various modified silicone oils described in "Modified Silicone Oil" technical data P6-18B published by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710), are effective. Silicone oils described in JP-A-62-215953 and JP-A-63-46449 are also effective. Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

[0170] As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
etc.), and other Japanese Patent Application Laid-open No. 54-48535, No. 62-
There are compounds described in No. 136641 and No. 61-88256. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

[0171] As a metal complex, US Pat. No. 42411
No. 55, No. 4245018, columns 3 to 36, No. 4254
No. 195, columns 3 to 8, JP-A-62-174741, JP-A No. 61-88256, pages (27) to (29), JP-A No. 63-1
No. 99248, Japanese Patent Application No. 62-234103, No. 62-
There are compounds described in No. 230595 and the like. Examples of useful anti-fading agents are disclosed in JP-A-62-215272 (12
It is described on pages 5) to (137).

[0172] The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. It's okay.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

[0174] A fluorescent brightener may be used in the light-sensitive material or the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. An example is K. Veenkataraman
ed. “The Chemistry of Synth”
etic Dyes” Volume V Chapter 8, JP-A-61-1
Examples include compounds described in No. 43752 and the like. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds. Optical brighteners can be used in combination with antifade agents.

Hardeners used in the constituent layers of light-sensitive materials and dye-fixing materials include US Pat.
No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, (exemplary compounds as shown in Chemical Formula 36, etc.),

0176
]

[C36]

Vinylsulfone hardeners (N,N'-ethylene-bis(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylolurea, etc.)
or polymeric hardeners (compounds described in JP-A No. 62-234157, etc.).

[0178] Various surfactants can be used in the constituent layers of the light-sensitive material and the dye-fixing material for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like. Specific examples of surfactants are JP-A-62-173463;
It is described in No. 62-183457 and the like.

[0179] The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static electricity, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17;
Fluorine surfactants described in JP-A-61-20944 and JP-A-62-135826, oily fluorine compounds such as fluorine oil, solid fluorine compound resins such as tetrafluoroethylene resin, etc. Examples include hydrophobic fluorine compounds.

[0180] A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 62-110065.

[0181] In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. It has functions such as promoting the movement of dye from the dye to the dye fixed layer, and from a physicochemical function, it is a base or base precursor, a nucleophilic compound, and a high boiling point organic solvent (oil).
, thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. A specific example is US Patent No. 45114
No. 93, JP-A No. 62-65038, etc.

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

[0185] In addition to the above, compounds capable of complex-forming reaction with the sparingly soluble metal compounds and metal ions constituting the sparingly soluble metal compounds described in European Patent Publication No. 210,660 and US Pat. No. 4,740,445 (complex-forming compounds Combinations of the following) and compounds that generate bases by electrolysis as described in JP-A No. 61-232451 can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

[0187] The development stopper mentioned here means that after proper development,
It is a compound that quickly neutralizes or reacts with a base to lower the base concentration in the film and stops development, or a compound that interacts with silver and silver salts to inhibit development. in particular,
Examples include acid precursors that release an acid when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors. For more details, please refer to JP-A No. 62-2531.
No. 59, pages (31) and (32).

[0188] As the support for the light-sensitive material and dye-fixing material of the present invention, those that can withstand processing temperatures are used. Common examples include paper and synthetic polymers (films). Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (e.g. triacetyl cellulose) or films containing pigments such as titanium oxide, and film-process synthetic paper made from polypropylene. , 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. are used. These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, supports described in JP-A-62-253159, pages (29) to (31) can be used.

[0189] A hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide are coated on the surface of these supports.
Carbon black or other antistatic agents may be applied.

[0190] Methods for exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, etc., exposing through reversal film or negative film using a printer or enlarger, etc. A method of scanning and exposing an original image through a slit using an exposure device of a copying machine, a method of transmitting image information to a light emitting diode, various lasers, etc. via an electric signal, and a method of transmitting image information to a CRT, liquid crystal display, etc. There is a method of outputting the image to an image display device such as an electroluminescence display or a plasma display and exposing it directly or via an optical system.

[0191] As a light source for recording an image on a photosensitive material,
As mentioned above, U.S. Patent No. 4 for natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc.
The light source described in column 56 of No. 500626 can be used.

Image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) )
, lithium iodate, BaB2 O4, etc., urea derivatives, nitroaniline derivatives, such as 3-methyl-4-nitropyridine-N-oxide (
Nitropyridine-N-oxide derivatives such as POM) and compounds described in JP-A-61-53462 and JP-A-62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

[0193] Further, the above image information may be obtained from a video camera,
Image signals obtained from electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels using a scanner, or an image signal created using a computer such as CG or CAD can be used.

[0194] The photosensitive material and/or dye fixing material is
It may also have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye. In this case, the transparent or opaque heating element is
-145544 specification etc. can be used. Note that these conductive layers also function as antistatic layers.

[0195] The heating temperature in the heat development step is about 50°C to about 250°C, but especially about 80°C to about 180°C.
°C is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular 50°C
More preferably, the temperature is about 10° C. lower than the temperature in the heat development step.

[0196] Dye migration can also be caused by heat alone,
A solvent may be used to facilitate dye transfer.

[0197] Also, JP-A-59-218443, JP-A No. 6
1-238056, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method,
The heating temperature is preferably at least 50°C and at most the boiling point of the solvent. For example, when the solvent is water, it is preferably at least 50°C and at most 100°C.

[0198] Examples of solvents used for accelerating development and/or transferring the diffusible dye to the dye fixed layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (such as As examples, those described in the section of image formation accelerators can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method in which they are applied to a dye fixing material, a photosensitive material, or both. The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

[0200] As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (
There is a method described on page 26). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

In order to promote dye transfer, a method may also be adopted in which a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is incorporated into the light-sensitive material or dye fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

[0202] Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere.

[0203] Layering the photosensitive material and the dye fixing material,
The pressure conditions and method of applying pressure when adhering to each other are described in Japanese Patent Application Laid-open No. 6
The method described in No. 1-147244, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic materials of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Utility Model Application No. 62-259
The apparatus described in No. 44 and the like is preferably used.

[0205]

[Examples] The present invention will be specifically explained below with reference to Examples.

Example 1 First, a method for preparing silver halide emulsions used in the present invention and comparative photothermographic materials will be described.

(1) Preparation of high-sensitivity emulsion (2) for blue-sensitive layer A well-stirred gelatin aqueous solution (2 gelatin in 770 ml of water)
0g, potassium bromide 3g, NaOH (1N) 6c
c and chemical compound 37 drug A 30mg, chemical compound 37 drug B45
(I) in Table 1)
The solution and solution (II) were added simultaneously over 30 minutes. After that, 6 cc of H2 SO4 (1N) was added, and Table 1
Solution (III) and solution (IV) were added simultaneously over 20 minutes. Further, a solution of the following sensitizing dye was added over a period of 16 minutes from 4 minutes after the start of addition of the solution (III).

[0208] After this, a desalting process was performed, and 20 g of gelatin was
was added to adjust the pH to 6.1 and pAg to 8.2, and then sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and chloroauric acid were added. Optimal chemical sensitization was performed at 58°C. In this way, a monodisperse cubic emulsion with an average grain size of 0.5 μm was obtained.

Dye solution: 160 mg of sensitizing dye A of chemical formula 38
80 mg of sensitizing dye B of Toka 38 in 3.5 cc of methanol
and a solution dissolved in 70 ml of water.

[0210]

[Table 1]

[0211]

[C37]

[0212]

[C38]

(2) Low-sensitivity emulsion for blue-sensitive layer ■ Preparation A well-stirred gelatin aqueous solution (20 gelatin in 770 ml of water)
g, 3 g of potassium bromide, 6 cc of NaOH (1N)
and chemical compound 37 drug A 30mg, chemical compound 37 drug B 150
solution (I) and solution (II) shown in Table 1 were added simultaneously over 30 minutes. Thereafter, 6 cc of H2SO4 (1N) was added, and then solutions (III) and (IV) shown in Table 1 were added simultaneously over a period of 20 minutes. Further, a solution of the following sensitizing dye was added over a period of 16 minutes from 4 minutes after the start of addition of the solution (III).

[0214] After this, a desalting process was performed and 20g of gelatin was added.
was added to adjust the pH to 6.2 and pAg to 8.2, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to adjust the pH to 6.2 and pAg to 8.2.
Optimally chemically sensitized at ℃. In this way, a monodisperse cubic emulsion with an average grain size of 0.35 μm was obtained.

Dye solution: 200 mg of sensitizing dye A of chemical formula 38
Toka 38 sensitizing dye B 100mg and methanol 4.5c
c. Solution dissolved in 90 cc of water.

(3) Preparation of high-sensitivity emulsion (2) for green-sensitive layer A well-stirred aqueous solution of gelatin (20 g of gelatin in 630 ml of water)
g, potassium bromide 0.30g, sodium chloride 6g
Solution I shown in Table 2 was added over 20 minutes to the mixture (15 mg of Chemical A of Chemical Formula 37 was added and kept at 55°C). Further, starting from 20 seconds after the start of addition of Solution I, Solution II shown in Table 2 was added over a period of 19 minutes and 40 seconds. Next, add 2 solutions of III and IV in Table 2.
The solution was added over a period of 0 minutes, and the following dye solution was added 1 minute after the completion of the addition.

[0217] After this, a desalting process was performed and 20g of gelatin was added.
was added to adjust the pH to 6.0 and pAg to 7.7, and then sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and chloroauric acid were added. Optimal chemical sensitization was performed at 68°C. In this way, a monodisperse cubic emulsion with an average grain size of 0.42μ was obtained.

[0218]

[Table 2]

Dye solution: 250 mg of the dye of chemical formula 39 was dissolved in 154 ml of methanol.

[0220]

[C39]

(4) Preparation of low-sensitivity emulsion (2) for green-sensitive layer A well-stirred aqueous solution of gelatin (20 g of gelatin in 610 ml of water)
g, potassium bromide 0.50g, sodium chloride 4g
The solution shown in Table 2 was added over 10 minutes. Also I
10 seconds after the start of liquid addition, Liquid II shown in Table 2 was added over a period of 9 minutes and 50 seconds. Next, add 20% of solution III and solution IV in Table 2.
The solution was added over several minutes, and 1 minute after the addition was completed, the following dye solution was added.

[0222] After this, a desalting process was performed and 20g of gelatin was added.
was added to adjust the pH to 6.0 and pAg to 7.6, and then sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and chloroauric acid were added. Chemical sensitization was optimally carried out at , 68°C. In this way, a monodisperse cubic emulsion with an average grain size of 0.27μ was obtained.

Dye solution: 300 mg of the dye of Chemical Formula 39 was dissolved in 154 ml of methanol.

(5) Preparation of highly sensitive emulsion (2) for red-sensitive layer A well-stirred gelatin aqueous solution (2 gelatin in 800 ml of water)
0g, potassium bromide 0.3g, sodium chloride 6g
, and 30 mg of chemical A of chemical formula 35 and kept at 65°C), solutions (1) and (2) in Table 3 were added at the same time for 30 minutes.
Addition was made at equal flow rates over a period of minutes. After that, (3
) and (4) were added simultaneously over 30 minutes. Furthermore, 160 ml of the following dye solution was added over a period of 20 minutes starting 3 minutes after starting addition of solutions (3) and (4) in Table 3.

[0225] After this, a desalting process was performed and 20g of gelatin was added.
was added to adjust the pH to 6.0 and pAg to 7.7, and then sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and chloroauric acid were added. , optimally chemically sensitized at 60°C. In this way, a monodisperse cubic emulsion with an average grain size of 0.5 μm was obtained. Dye solution: 67 mg of dye (a) of Chemical Formula 40 and 133 mg of dye (b) of Chemical Formula 40 were dissolved in 100 ml of methanol.

[0226]

[Table 3]

[0227]

[C40]

(6) Preparation of low-sensitivity emulsion (2) for red-sensitive layer A well-stirred gelatin aqueous solution (2 gelatin in 800 ml water
0g, potassium bromide 0.3g, sodium chloride 6g
, and 30 mg of chemical compound A (chemical formula 37) and kept at 40°C), solutions (1) and (2) in Table 3 were added at the same time for 30 minutes.
Addition was made at equal flow rates over a period of minutes. After that, (3
) and (4) were added simultaneously over 30 minutes. Furthermore, 220 ml of the following dye solution was added over 20 minutes starting 3 minutes after the start of addition of solutions (3) and (4).

[0229] After this, a desalting process was performed and 20 g of gelatin was added.
was added to adjust the pH to 6.0 and pAg to 7.7, and then sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and chloroauric acid were added. , optimally chemically sensitized at 60°C. In this way,
A monodisperse cubic emulsion with an average grain size of 0.31μ was obtained.

Dye solution: 67 mg of the dye (a) of chemical formula 40 and 133 mg of the dye (b) of chemical formula 40 are mixed in 100 ml of methanol.
dissolved in.

Next, a method for preparing a dispersion of zinc hydroxide will be described.

[0232] 12.5 g of zinc hydroxide with an average particle size of 0.15 μm, 1 g of carboxymethyl cellulose as a dispersion, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution and milled with an average particle size of 0.75.
It was ground for 30 minutes using mm glass beads. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent (a) will be described. 10 g of electron transfer agent (a), 0.5 g of polyethylene glycol and nonylphenyl ether as a dispersant, 0.5 g of Demol N manufactured by Kao Soap Co., Ltd.
was added to a 5% aqueous gelatin solution and milled to reduce the average particle size to 0.7.
Grinding was performed for 60 minutes using 5 mm glass beads. Separate the glass beads and add an electron transfer agent (
A dispersion of a) was obtained. In addition, the electron transfer agent (a) is chemical compound 33
(X-2).

Next, a method for preparing a gelatin dispersion of a dye-providing compound will be described.

[0235] Each of yellow, magenta and cyan was heated and dissolved at about 60°C as per the prescription in Table 4.
A homogeneous solution was obtained. 10 of this solution and lime-processed gelatin
% aqueous solution, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of a dye-providing compound.

[0236]

[Table 4]

In Table 4, dye-providing compound (1)
, (2) are (1) and (2) shown in Chemical Formula 16, respectively, and the dye-providing compound (3) is (3) shown in Chemical Formula 17.
). Furthermore, the electron donor (1) is represented by chemical formula 28 (ED-9), and the compound (5) is represented by chemical formula 30 (ED-15). Further, the high boiling point solvent (2) is shown by chemical formula 41, the electron transfer agent precursor (3) is shown by chemical formula 42, and the compound (4) is shown by chemical formula 43.

[0238]

[C41]

[0239]

[C42]

[0240]

[C43]

Next, a method for preparing a gelatin dispersion of the electron donor (6) for the intermediate layer will be described.

Electron donor (6) [Chemical formula 30 (ED-16
)] 20.0g (ED-17)5 shown in chemical formula 30
．． 9g, 1.8g of compound (8) of chemical formula 44, 8.5g of high boiling point solvent (2) of chemical formula 41, and 30m of cyclohexanone
1 and heated to dissolve at 60°C to form a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, 0.8 g of sodium dodecylbenzenesulfonate, 0.3 g of sodium bisulfite, and 30 ml of water were stirred and mixed, and then dispersed using a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a gelatin dispersion of electron donor (6).

[0243]

[C44]

Using the above emulsion dispersion, a coating solution was prepared as follows.

First layer (red-sensitive emulsion layer) Photosensitive silver halide emulsion ■ 300 g and photosensitive silver halide emulsion ■
96 ml of water was added to 880 g and dissolved at 38°C. Next, 260 ml of a 0.15% aqueous solution of the antifoggant (9) of Chemical Formula 45 was added, and after 5 minutes, 3500 g of a gelatin dispersion of a cyan dye-providing compound dissolved at 45°C was added.
, 62 ml of a 3% aqueous solution of thickener (10) of Chemical Formula 46 was added to prepare a coating solution for the first layer.

[0246]

[C45]

[0247]

[C46]

[0248] Second layer (middle layer) lime-treated gelatin 14
% aqueous solution and 599 g of the gelatin dispersion of the electron donor (6) in 43 above were added and dissolved at 38°C. Next, 715g of zinc hydroxide dispersion was dissolved at 45℃,
Furthermore, 50 ml of a 5% aqueous solution of the anionic surfactant (11) of Chemical Formula 47, and 2 ml of a 5% aqueous solution of the compound (12) of Chemical Formula 48.
31 ml, 231 ml of 5% aqueous solution of polyvinyl alcohol (degree of polymerization 2000), 12 of compound (13) of chemical formula 49
% latex dispersion, 462 ml, thickener of formula 46 (10
) was added to prepare a coating solution for the second layer.

[0249]

[C47]

0250]

[C48]

[0251]

[C49]

Third layer (green-sensitive emulsion layer) Photosensitive silver halide emulsion ■ 350 g and photosensitive silver halide emulsion ■
1016 g was dissolved at 38°C, 289 ml of a 0.15% aqueous solution of the antifoggant (9) of Chemical Formula 45, 300 ml of a 1% aqueous solution of potassium bromide after 5 minutes, and a gelatin dispersion of a magenta dye-donating compound after another 5 minutes. 4171g was dissolved at 45°C and added, and a thickener (10) of chemical formula 46 was added.
121 ml of a 3% aqueous solution was added to prepare a coating solution for the third layer.

0253 4th layer (middle layer) Lime-treated gelatin 14
% aqueous solution, 823 g of electron transfer agent (a) [(X-
2)] and 590 g of the above gelatin dispersion of electron donor (6) were added with 1312 ml of water.
It was dissolved at 8°C. Next, 5 of the surfactant (11) of chemical formula 47
% aqueous solution 49 ml, 138 ml of 5% aqueous solution of compound (12) of Chemical Formula 49, 177 ml of 5% aqueous solution of dextran,
115 ml of a 3% aqueous solution of the thickener (10) of Chemical Formula 46 was added to prepare a coating solution for the fourth layer. The pH of this coating solution was 40°C.
It was 6.8.

5th layer (blue-sensitive emulsion layer) Photosensitive silver halide emulsion ■ 336g and photosensitive silver halide emulsion ■
Dissolve 1060 g at 38°C, add 250 ml of a 0.14% methanol solution of antifoggant (14) of chemical formula 50, add 168 ml of a 1% aqueous solution of potassium bromide after 5 minutes, and after another 5 minutes add a yellow dye-donating compound. 3819g of gelatin dispersion was dissolved at 45℃ and added, and further
117 ml of a 3% aqueous solution of the thickener (10) in No. 6 was added to prepare a coating solution for the fifth layer.

0255]

[C50]

0256 Layer 6 (protective layer) Lime-treated gelatin 14
% aqueous solution 890g, gelatin dispersion of silica matting agent (
81g of silica (8g of average particle size 3μ dispersed in 8% gelatin aqueous solution) was heated and dissolved at 38°C, 1110g of zinc hydroxide dispersion dissolved at 45°C was added, and the surfactant of chemical formula 47 was added. 5% aqueous solution of agent (11) 9
8 ml, 10% aqueous solution of compound (15) of chemical formula 51 244
ml, 151 ml of a 5% aqueous solution of dextran, and 23 ml of a 3% aqueous solution of the thickener (10) of Chemical Formula 46 were added to prepare a coating solution for the sixth layer.

0257]

[C51]

[0258] Using the above coating solution, coat the first to sixth layers on a support of polyethylene terephthalate (thickness 100 μm, with a carbon black antihalation layer as a back layer) so that the wet film thickness is as shown in Table 5. A photosensitive material 101 was prepared by applying a layer coating solution.

0259]

[Table 5]

In the photosensitive material 101, as shown in Table 6, the acetylene compound of the present invention of chemical formula 2, II-2 of chemical formula 4, and chemical compound 6 were added to the coating solutions of the first layer, third layer, and fifth layer. I of
I-11 and II-19 of chemical formula 8 were dissolved in methanol and added to prepare comparative photosensitive materials 102 to 102.
I made 104.

[0261]

[Table 6]

In the photosensitive material 101, as shown in Table 7, the acetylene compound of the present invention represented by Chemical Formula 2, II-2 of Chemical Formula 4, and II-2 of Chemical Formula 6 were added to the coating solutions of the second layer, fourth layer, and sixth layer. II
-11 and II-19 of Chemical formula 8 were dissolved in methanol and added to the comparative photosensitive materials 105-1.
I made 07.

0263

[Table 7]

Next, as the acetylene compounds of the present invention represented by Chemical Formula 2, II-1, II-2, II-4 represented by Chemical Formula 4, and I represented by Chemical Formula 6 are used.
I-11, II-18 and II-19 of chemical formula 8 were used, and gelatin dispersions Y-1 to Y-1 of dye-providing compounds were used.
Y-6, M-1 to M-6, and Cy-1 to Cy-6 were made as follows.

[0265] Yellow, magenta, and cyan were dissolved by heating at about 60°C according to the prescriptions shown in Tables 8 to 10 to form a uniform solution. After stirring and mixing this solution with 100 g of a 10% aqueous solution of lime-treated gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water, the mixture was heated in a homogenizer for 10 minutes at 10,000 rpm.
Dispersed at m.

0266]

[Table 8]

0267]

[Table 9]

0268

[Table 10]

[0269] The compounds shown in Tables 8 to 10 are as follows:
Same as in Table 4.

[0270] In the photographic material 101, the gelatin dispersions of yellow, magenta, and cyan dye-providing compounds in the formulation in Table 4 were replaced with those in the formulations in Tables 8 to 10. Photosensitive material 108-1
I made 13.

Photosensitive materials 101 to 113 had the same structure and were coated immediately after preparing the coating solution, and
Two types of samples were prepared, one in which the coating solution was kept at 40° C. for 16 hours and then coated.

[0272] In preparing the photosensitive materials 101 to 113, the compound (A) represented by Chemical Formula 52 and (
A 4% aqueous solution of a 3:1 mixture with B) was added at a rate of 7% of the flow rate of the fourth layer coating solution.

0273

[C52]

Next, an image receiving material was prepared as shown in Table 11.

0275]

[Table 11]

In Table 11, the support (1) has a structure as shown in Table 12, and the compounds include silicone oil shown in Chemical formula 53, surfactant shown in Chemical formula 54, and mordant. Chemical formula 55 is a high boiling point solvent, chemical formula 56 is a high boiling point solvent, and chemical formula 57 is a hardening agent.

0277]

[Table 12]

[0278]

[C53]

0279]

[C54]

0280]

[C55]

0281]

[C56]

0282]

[C57]

[0283] The matting agents, water-soluble polymers, and optical brighteners in Table 11 are as shown below. Matting agent (1); Silica matting agent (2); Benzoguanamine resin (average particle size 15
μ) Water-soluble polymer (1); Sumikagel L5-H (manufactured by Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2); Dextran (molecular weight 70,000) Fluorescent brightener (1); 2,5-bis(5- Tertiary butylbenzoxazolyl (2)) Thiophene and above photosensitive materials 101 to 113 and image receiving materials were patented in 1983-1371.
It was processed using the image recording apparatus described in No. 04.

[0284] That is, the original image [a test chart in which wedges of Y, M, Cy, and gray whose density changes continuously are recorded] is scanned and exposed through a slit.
The exposed light-sensitive material was immersed in water kept at 40° C. for 5 seconds, squeezed with a roller, and then immediately stacked on top of the image-receiving material so that the film surface was in contact with the film surface. The film was heated for 15 seconds using a heat drum whose temperature was adjusted so that the temperature of the surface of the water-absorbed film was 78°C, and when it was peeled off from the image-receiving material, a clear color image corresponding to the original image was obtained on the image-receiving material.

Table 13 shows the results of measuring the maximum density of cyan, magenta, and yellow in the gray area.

0286]

[Table 13]

As is clear from the results in Table 13, the photosensitive material of the present invention has a particularly high maximum density, and the maximum density does not decrease even after keeping the coating solution at 40° C. for 16 hours, making it possible to produce it in large quantities. It can be seen that this is a heat-developable photosensitive material suitable for.

0288

According to the present invention, a positive image with a high maximum density can be obtained even if the coating solution is manufactured using a coating solution that has been kept warm. Therefore, the photosensitive material is suitable for mass production.

Claims (1)

[Claims] 1. A heat-developable color photosensitive material comprising on a support at least a photosensitive silver halide, a binder, an electron transfer agent, an electron donor, and a reducible dye-donating compound that releases a diffusible dye upon reduction. , wherein at least one photosensitive layer containing the photosensitive silver halide contains the compound of formula 1 together with the reducible dye-providing compound dispersed in the binder as the same emulsion. A heat-developable color photosensitive material. [Formula 1] [In Chemical Formula 1, L represents a simple bond or a divalent linking group. n represents an integer from 1 to 4. R1 when n=1
represents a hydrogen atom, carboxyl group, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group. When n=2, 3 or 4, R1 represents a divalent, trivalent or tetravalent residue. R2 represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl group, a heterocyclic group, or a carbamoyl group. When n is 2, 3 or 4, L and R
Each combination of 2 may be the same or different. However, this excludes the case where L is a simple bond and when n=1, both R1 and R2 are hydrogen atoms. ]