JPH03238453A - Heat-developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a positive image high in maximum density by incorporating an N-containing heterocyclic compound having a mercapto group in at least one of photosensitive layers and a specified compound in at least one of nonphotosensitive layers. CONSTITUTION:At least one of the photosensitive layers contains the N- containing heterocyclic compound having a mercapto group in at least one of the photosensitive layers and at least one of the nonphotosensitive layers contains at least one of the compounds represented by formula I in which L is a simple bond or a divalent bonding group; n is an integer of 1 - 4, and when n is 1, R1 is H, carboxy, or the like, and when n is 2, 3, or 4, R1 is a di-, tri, or tetra-valent residue, and R2 is H, carboxy, or the like, thus permitting a positive image high in maximum density to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat-developable color photosensitive material, and particularly to a heat-developable color photosensitive material capable of obtaining a positive image with a high maximum density. .

(Background Art) Heat-developable photosensitive materials are well known in this technical field, and for more information on heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography! ! (Published by Corona Publishing, I982), pages 242 to 255, US Pat. No. 4,500,626, etc.

Many methods have also been proposed for obtaining positive color images by heat development.

For example, in US Pat. No. 4,559,290, so-called DDR
An oxidized compound that does not have the ability to release dye is made to coexist with a reducing agent or its precursor, and the reducing agent is oxidized according to the amount of exposure of silver halide through heat development, and the reducing agent that remains unoxidized is A method has been proposed in which a diffusible dye is released by reduction. Also, European Patent Publication No. 22074
No. 6, Kokai Technical Report 87-6199 (Vol. 12, No. 22) describes N as a compound that releases a diffusible dye by a similar mechanism.
A heat-developable color photosensitive material using a non-diffusible compound which releases a diffusible dye by reductive cleavage of a -X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) is described.

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 together as the reducing agent.

(Problem to be solved by the invention!!!i) 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 the unexposed areas are However, since this reduction reaction occurs, there is a problem in that the maximum density of a positive image decreases.

Therefore, an object of the present invention is to provide a heat-developable photosensitive material from which a positive image with a high maximum density can be obtained.

Incidentally, Jikai No. 1-222256 describes a heat-developable photosensitive material that uses a mercapto compound or an acetylene compound and provides a positive image with a high maximum density. There is no indication that particularly high maximum concentrations can be obtained when these compounds are used in each particular layer.

(Means for Solving the Problems) In order to achieve the above object, the heat-developable photosensitive material of the present invention includes at least a photosensitive silver halide, a binder, an electron transfer agent, an electron donor, and a reduced material on a support. In a heat-developable photosensitive material having a reducible dye-providing compound that releases a diffusible dye, at least one photosensitive layer contains a nitrogen-containing heterocyclic compound having a mercapto group, and at least one non-photosensitive layer contains a nitrogen-containing heterocyclic compound having a mercapto group. A compound represented by the following general formula (I) is added to the sexual layer in 1111! This is a heat-developable photosensitive material containing the above.

The acetylene compound preferably used in the present invention is represented by the following general formula (I).

General formula (I) %Formula%) In the above general formula (I), L is a simple bond or 2
represents a valence linking group, n represents an integer of 1 to 4, n=1
When R1 is a hydrogen atom, a carboxyl group, or each substituted or unsubstituted alkyl group, cycloalkyl group,
It represents an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and when n=2.3 or 4, R+ represents a divalent, trivalent, or tetravalent residue, respectively.

R1 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.

When n is 2.3 or 4, -t and -c=c-R2 may be the same or different. However, this excludes the case where L is a simple bond and when n=1, R1 and R2 are both hydrogen atoms.

First, general formula (I) will be explained in detail.

The alkyl group of R,, R, may be linear or branched, and examples of the alkyl group include butyl group, isobutyl group,
Hexyl group, heptyl group, octyl group, dodecyl group, pentadecyl group, etc. Examples of substituents for substituted alkyl groups include alkoxy group (e.g. methoxy group, etc.), aryloxy group, acyloxy group, heterocyclic oxy group. , hydroxy group, carboxyl group or its salt, formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, sulfino group or its salt, sulfo group or a salt thereof, an alkylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a substituted or unsubstituted sulfamoyl group, an alkoxysulfonyl group, an alkyl sulfonyl group, an acylamino group, a 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, cyclo alkyl group,
alkenyl group, aryl group, aralkyl group, heterocyclic group,
Alkynyl 1& (for example, ethynyl group), and the like. There may be two or more of these substituents.

Examples of cycloalkyl groups for R and R1 include nclopentyl group, cyclohexyl group, and decahydronaphthyl group; examples of alkenyl groups include propenyl group, isopropenyl group, and styryl group; examples of alkynyl groups include:
Ethynyl group, phenylethynyl group, etc.: Examples of aralkyl groups include benzyl group, phenethyl group, etc.

These groups may have the substituents described for the alkyl group, and may have two or more direct substituents.

Examples of aryl groups for R and R include phenyl groups and naphthyl groups, and examples of substituents for substituted aryl groups include alkyl groups (methyl groups, dodecyl groups, etc.), alkenyl groups, and aryl groups. , cycloalkyl group, aralkyl group, alkynyl group, cyano group, nido group, nitroso group,
Substituted or unsubstituted amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group, hydroxyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, hetero ring oxy group,
Acyloxy group, heterocyclic group (5-6M ring, preferably nitrogen-containing heterocycle), alkinosulfonyl group, aryloxysulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, mercapto group, formyl group group, acyl group, alkylsulfonyl group, arylsulfonyl group, carboxylic acid group or its salt, sulfone group or its salt, sulfino group or its salt, halogen atom (fluorine, bromine, chlorine, iodine)
, a substituted or unsubstituted ureido group, carbamoyl group, sulfamoyl group, etc. These substituents may be further substituted. Furthermore, there may be two or more substituents inverted upward.

The R,,R,i elementary ring group is preferably a 5- or 6-membered ring group, such as furyl group, thienyl group, henzochenyl group, pyridyl group, and quinolyl group. These heterocyclic groups may have the same substituents as the above substituted aryl group.

Examples of the aryloxycarbonyl group for R1 include phenoxycarbonyl, and examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl groups.

Examples of the carbamoyl group for R include, in addition to -CONHi, a carbamoyl group substituted with the above-mentioned substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.

When n is 2.3 or 4, R2 represents a divalent, trivalent or tetravalent residue, such as the above-mentioned R or R
Examples include groups obtained by removing one, two, or three hydrogen atoms from the monovalent group (2). Moreover, -NH- is also included in R2 when n=2.

L is a simple bond or a divalent linking group (preferably 1 represents -0-C- group or -CONH- group).

n is preferably l or 2.

Among these, compounds in which one of R and R is a hydrogen atom and the other is a group other than a hydrogen atom are preferred.

More preferably, one of R and R is a hydrogen atom, and the other is a phenyl group or a substituted phenyl group. Particularly preferred are compounds represented by the following general formula (n).

General formula (n) where m is 1 or 2 1IR3 is m-1,
Alkyl group, cycloalkyl group having 1 to 20 carbon atoms,
It represents an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group, and when m-2 represents an alkylene group, an arylene group, or a cycloalkylene group, and these substituents may further include other direct substituents. It is also possible to convert it directly.

Hereinafter, R3 will be explained in detail.

In the case of an alkyl group, it may be straight chain or branched, and examples of alkyl groups include propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, heptyl group, isoheptyl group. 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, and alkoxy groups. , aryloxy group, acyloxy group, heterocyclic oxy group, carboxyl group or its salt, formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, ryoroxycarbonyl group, cyano group, mercapto group , alkylthio group, arylthio group, sulfino group or its salt, sulfo group or its salt, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, oxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylalkylsulfonylamino group, arylsulfonylamino group,
Substituted or unsubstituted sulfamoylamino group, nitro group, nitroso group, etc. Two or more of these groups may be present, and the substituents may be further substituted.

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

Examples of aryl groups include phenyl groups and naphthyl groups, and examples of direct substituents for substituted aryl groups include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and heterocyclic groups. group (5- to 6-membered ring, preferably nitrogen-containing heterocycle), halogen atom (
-fluorine, chlorine, bromine, iodine), hydroxyl group, alkoxy group, aryloxy 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, alkylsulfonyl group, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryl Oxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonyl group, alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group, nitro group, nitroso group, etc. These substituents may be further substituted, and two or more substituents as shown above may be present.

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,
Examples include furyl group, thienyl group, benzothienyl group, pyridyl group, and quinoline group.

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 (0-2-1p-)phenylene group, (l, 4
Examples of cycloalkylene groups include cyclohexylene groups and the like. 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, R1 is preferably an alkyl group or a cycloalkyl group having 3 or more carbon atoms.

More preferably, R1 is an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group.

Specific examples of the present invention are shown below.

-1 -2 ■ ■-10 C! H5 ■ ■-11 ■-12 ■ J[-13 ■ C*H,5 C)1. H.

l-14 ■-18 ■ 5 -19 l-16 ■-20 I-IT ■ 1 ■-22 ■ 3 ■-24 The acetylene compound of the present invention is a condensation of the following 4-ethynylaniline and an acid chloride of a carboxylic acid. easily obtained from the reaction.

0℃ I Also, 4-ethynylaniline is HELVETICA CH
IMICAACTA 549 2066 pages (I971
It can be synthesized by the method described in 2010).

The acetylene compound used in the present invention can be dissolved in a water-soluble organic solvent (for example, methanol, ethanol, acetone, dimethylformamide, etc.) or a mixed solution of this organic solvent and water to form a non-photosensitive layer (intermediate layer, etc.). (protective layer, etc.). Particularly preferably, the acetylene compound is added to an intermediate layer provided between photosensitive layers having different color sensitivities. A heat-developable photosensitive material having three photosensitive layers having three mutually different color sensitivities is usually provided with two intermediate layers, and it is preferable that an acetylene compound is added to both of the intermediate layers.

Furthermore, the acetylene compound used in the present invention can be incorporated into the binder by dissolving a high boiling point organic solvent in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary. . Further, the acetylene compound used in the present invention can also be dispersed and contained in the binder in the form of fine particles.

The content of acetylene compound is 1O per 1rrf of additive layer.
-4 mol to 1 mol, especially 10-3 mol -5X10-' mol are preferred.

Next, the nitrogen-containing heterocyclic compound having a mercapto group used in the photosensitive layer will be explained.

As a nitrogen-containing heterocyclic compound having a mercapto group,
A compound represented by the following general formula (It) is preferred.

A 5-, 6-, or 9-membered heterocycle containing a general formula or a sulfur atom is preferred, and the term "heterocycle" herein also includes those fused with a benzene nucleus or a naphthalene nucleus.

Preferred examples are listed below.

z (However, Y is a 5-, 6-, or 9-membered hetero (complex)
5j! The ring completed by Y in the above general formula (I) contains at least one nitrogen atom! , 6j! or a 9-membered heterocycle, particularly containing two or more nitrogen atoms, or one or more nitrogen atoms and an oxygen atom, where Z is a hydrogen atom,
The group includes a group selected from an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, and an aralkyl group, and these groups may have a suitable substituent.

Further, the carbon atoms forming the above ring structure may be substituted with other substituents other than hydrogen atoms. Examples of substituents for Z and substituents for the carbon atoms forming the above ring structure include halogen Atom, nitro group, cyano group, hydroxyl group, amino group, substituted amino group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxyl group, aryloxy group, acyl group, alkoxycarbonyl group, acylamino group, carbamoyl group,
Examples include N-substituted carbamoyl group, sulfamoyl l, N-substituted sulfamoyl group, sulfonyl group, carboxyl group, and sulfone # group.

Specific examples of the nitrogen-containing heterocyclic compound having a mercapto group of the present invention are listed below.

■ ■ 1[[-3 ■ ■ ■ ■ ■ ■ 7 ■ 8 ■ 9 ■ 0 ■ 1 ■ 2 ■ 3 ■-24 1-9 ■-11 ■=13 ll-15 ■ 5 ■ 7 ■ 9 ■-31 ■-10 1[[-12 ■ 4 ll-16 ■ 6 ■ 8 ■ 0 ■ 2 Shi ■ko ■ 33 ■-35 ■-37 ■ 9 111-48 ■ 0 ■ 2 ■ 4 ■ 6 ■ 8 ■ 0 Sushi 3Nt(n) ■-49 ■-51 ■ 3 0ONa 1-41 -42 -43 ■-44 ■ 5 ■ 6 ■-47 )υtall.

■-54 ■ 5 ■ 6 ■ 7 ■ 8 ■ 9 ■-60 ■-61 ■-62 ■ 3 ■ 4 ■-65 ■ 6 ■ 7 ■ 8 ■ 9 ■ 0 ■ QC)IzCHlOH ■ 0 ■ 1 ■ 2 ■ 3 ■ 4 ■-85 2 ■ 3 ■-74 ■ 5 ■ 6 ■-77 ■ 8 ■ 9 υshi II3 ■ 6 ■ 7 ■ 8 ■ 9 ■ 0 ■ 1 1 ■-92 ■-93 ■ 4 ■ 5 ■ 6 ■ 02 ■ 03 ■ 04 lll-105 ■-97 ■ 8 ■ 00 ■ 06 III-108 m-it.

■ ■-99 ■ 01 ■ 07 ■ 09 l1l-112 III-116 Iff-113 t-117! [[-114 III-118 I[[-115 Such compounds may be used alone or in combination of two or more.

The amount added is 10-" per mol of photosensitive silver halide.
The nitrogen-containing heterocyclic compound having a mercapto group may be used in an amount of ~10-1 mol, preferably 10-4 to 10-'' mol, in at least one of the color-sensitive layers, preferably in all of them. Add to the sexual layer.

In the present invention, the above-mentioned compound can be added at any step of the photographic emulsion manufacturing process, or at any stage after manufacturing the photographic emulsion and immediately before coating, but usually,
In the present invention, it is preferable to add the photographic emulsion at any stage after the production of the photographic emulsion and immediately before coating. A combination of three silver halide emulsion layers each having a light-sensitive layer in a different spectral region.For example, a combination of three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. There are combinations of photosensitive layers. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials. Furthermore, each of these photosensitive layers may be divided into two or more layers, if necessary.

The heat-developable photosensitive material of the present invention can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back 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 general formula (C-I).

PWR-(Time)t-Dye represents a group that releases Dye through a subsequent reaction after being released as the general formula (C-L), t represents an integer of O or l.

Dye represents a dye or its precursor.

First, PWR will be explained in detail.

PWR is US Pat. No. 4,139,389, or US Pat. No. 4,139,379, US Pat. No. 4,564.577,
Electron-accepting center and intramolecular nucleophilic substitution reaction in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-59-185333 and JP-A-57-84453 It may correspond to the part including the center, or it may correspond to the part including the center, or as described in U.S. Patent No. 4,232,107, Japanese Patent Application Laid-Open No. 59-101649, Research Disclosure (I984) IV, No. 24025, or Japanese Patent Application Laid-Open No. 61-88257. As disclosed, it corresponds to a part containing an electron-accepting quinonoid center and a carbon atom linking it to the photographic reagent in a compound that releases the photographic reagent by an electron transfer reaction in the molecule after being reduced. There may be one, and Japanese Patent Publication No. 56-14253
No. 0, U.S. Patent No. 4,343,893, U.S. Patent No. 4,619,
884, in which the single bond is cleaved to release the photographic reagent, an aryl group substituted with an electron-withdrawing group and the atom connecting it to the photographic reagent (
may correspond to a moiety containing a sulfur atom, a carbon atom, or a nitrogen atom), and also as described in U.S. Pat.
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 that connects the photographic reagent with the nitro group, as disclosed in No. 223, It corresponds to the geminal dinitro moiety in the dinitro compound that beta-desorbs the photographic reagent after accepting electrons and the moiety containing the carbon atom that connects it to the photographic reagent described in U.S. Pat. No. 4,609.61O. It's okay.

Also, more preferably, European Patent No. 220.7
No. 46A2, Published Technical Report 87-6199, U.S. Patent No. 4,
No. 783.396, Japanese Patent Publication No. 63201653, 63
-201654 etc., N-X bond (
A compound having an electron-withdrawing group (X represents an oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group; A compound having a P○-X bond in one molecule described in JP-A No. 63-271344 (X has the same meaning as above)
and a compound having an electron-withdrawing group, JP-A-63-2713
No. 41 describes a c-x' bond within one molecule (X' is synonymous with X.

) and a compound having an electron-withdrawing group.

Also, Japanese Patent Application No. 62-319989, No. 62-3207
Compounds described in No. 71 that release a diffusible dye by cleavage of a single bond after reduction due to a π bond conjugated with an electron-accepting group can also be used.

In order to more fully achieve the object of the present invention, the general formula (C
-1], those represented by the general formula (CII) are preferred.

General formula CCT1] (Time)-t Dye binds to at least one of RIOI, RIOI, or EAG.

The portion corresponding to PWR in the general formula (CI[] will be explained.

X represents a group (-N (RIo'')-) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

RIOI, R161 and Rloz represent a group other than a hydrogen atom or a simple bond.

Examples of groups other than hydrogen atoms represented by R1111, R1@ffi, and R103 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryol groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, and sulfamoyl groups. , these may have a substituent.

R101 and RI03 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc. R10
1 and RIos preferably have 1 to 40 carbon atoms.

R101 is preferably a substituted or unsubstituted acyl group or sulfonyl group, and examples thereof are the same as the acyl group and sulfonyl group described for RIOI and R1113. The number of carbon atoms is preferably 1 to 40.

Rlol, Rloz and R103 may be bonded to each other to form a 5- to 6-membered ring.

As X, enzymes are particularly preferred.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula (C1l
) Among the compounds represented by the formula (CI[l), those represented by the general formula (CI[l) are preferred.

General formula (CI) EAC (Time)-t Dye is bonded to at least one of R"' and EAG.

X has the same meaning as above.

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

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. As EAG, a group represented by the following -a formula [A] is preferable.

General formula [A] In general formula (A), Z represents -C-5ub or -N-.

v7 represents an atomic group forming a mi- to six-membered aromatic group together with Z+ and Zt, and n represents an integer from 3 to 3.

VziZs-1Va; Z3 Z4-1■.

; Z3 Za Zs -1V*;
Zs Z4Z s Z &-1Vt; Zs
'1m Zs '1bZt-1Vs; Z3
Za Zs Zh Zt2@-.

Sub 5ub Z and -L each represent -C--N--Oub S-1 or -SO,-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Even if each Sub is the same,
Each of them may be different, or each may be bonded to each other to form a 3- to 6-membered saturated or unsaturated carbocycle or heterocycle.

In general formula [A], the sum of the Hammett substituent constant sigma variations of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0°85 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 EAC can be used to adjust the physical properties of the entire chemical compound. Examples of physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, and reaction with nucleophilic groups. It can be used to adjust the properties, reactivity toward electrophilic groups, etc.

A specific example of an EAG is described in European Patent Publication No. 220746A2, pages 6-7.

Time may lead to the cleavage of nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bonds, resulting in D
Represents a group that releases ye.

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244.
No. 36549 (8) pages - 04, patent application No. 61-8862
Examples include the groups described on pages 5 (36) to (44).

Dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl groups, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. Note that these dyes can also be used in the form of a temporarily shortened wavelength that can be multicolored during development.

Specifically, EP76.492A, JP 591650
Dye disclosed in No. 54 can be used.

The compound represented by the above general formula [C■] or (CI[[) must itself be immobile in the photographic layer,
For this purpose, EAG, R"', R""RI11' or
position (especially the EAG position) with a carbon number of 8 or more)
It is desirable to have an IF.

Typical specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited thereto, and is described in European Patent Publication No. 220746A2, Publication No. 87-6199, etc. Dye-providing compounds that have been described can also be used.

L(JNMC1hH3a(I1) (I1) (I2) (I0) R: CH.

(I5) (I6) C13Hz.

Each of these compounds can be prepared by the methods described in the patent specifications cited above.

The amount of the dye-donating compound to be used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol/bo, preferably 0.05 to 5 mmol/bo. l~3
It is in the mmol/bo range. The dye-donating substances can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 51, mobile dyes having different hues, for example, at least one of cyan, magenta, and yellow dye-providing substances are mixed and contained in a layer containing silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of dye-providing substances that emit .

In the present invention, an electron donor and an electron transfer agent (ETA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Publication No. 876199, and the like. Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula (C) or CD).

General Formula [C] General Formula CD) In the formula, A1° and A. 2 each represents a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophile.

Here, examples of nucleophilic reagents include OHe, Roe (R; alkyl group, aryl group, etc.), hydroxamic acid anion!
Examples include anionic reagents such as 1sO3"e, and compounds having lone pairs of electrons such as primary or secondary amines, hydrazine, hydroxylamines, alcohols, and thiols.

Preferred examples of A1゜I and Al01 are hydrogen atoms,
Acyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoryl group, dialkylphosphoryl group, or JP-A-59-197037, JP-A-59-2
It may be a protecting group disclosed in No. 0105, or A
l61, AH02 is NihaR when possible! 61, R
161, RNO3 may be combined with R264 to form a ring. Further, A1°3 and AlO2 may be the same or different.

Rio+, Rxoz, Rzo3 and R204
are hydrogen atoms, alkyl groups, aryl groups, alkylthio groups, arylthio groups, sulfonyl groups, sulfo groups,
These groups represent a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amido group, an imido group, a carboxyl group, a sulfonamido group, etc., and these groups may have a substituent group if possible.

However, the total carbon number of R11 to Rx*a is 8 or more. Furthermore, in the general formula (C), Rxoz and Rt@t and/or R803 and R204 are combined with each other to form a saturated or unsaturated ring. Good too.

Among the electron donors represented by the general formula (C) or CD), those in which at least two of Rzo+ to R1114 are substituents other than hydrogen atoms are preferable, and particularly preferable compounds include at least one of R2111 and Rzoz,
and at least one of R103 and Rtera is a substituent other than a hydrogen atom.

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 invention is not limited to these compounds.

(ED-1) (ED-2) (ED-3) (ED H (ED (ED 6) (ED 10) H H3 (ED 7) (ED 11) 14 (ED-8) +111 H (ED-12) (ED 9) υH l13 (ED-13) However, movable ones are preferable.

A particularly preferred ETA has the following general formula (X=I) or [
This is a compound represented by Xn).

The amount of υH electron donor (or its precursor) to be used has a wide range, but is preferably 0.0 per mole of positive dye-donating substance.
A preferred range is from 1 mol to 50 mol, particularly from 0.1 mol to 5 mol. Also, 0.0% per mole of silver halide.
001 mol to 5 mol, preferably 0.01 mol to 1.5 mol
It is a mole.

As the ETA used in combination with these electron donors, any compound can be used as long as it is oxidized by silver halide and the oxidized form has the ability to cross-oxidize the electron donor (X- 1) (X-If) In the formula, R represents an aryl group, R"l, RoxR"
", R30', R"% and R"" are hydrogen atoms,
It represents a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and may be directly substituted if possible, and these may be the same or different.

In the present invention, compounds represented by the general formula (X-1t) are particularly preferred. In the general formula (X-n), R ramit , , Rs*g 5Rxo and Rgo 4 are a hydrogen atom, a carbon Preferred are alkyl groups of 1 to IO, substituted alkyl groups of 1 to 10 carbon atoms, and substituted or unsubstituted aryl groups, and more preferred are hydrogen atoms, methyl groups, hydroxymethyl groups, phenyl groups, hydroxyl groups, alkoxy groups,
It is a phenyl group substituted with a hydrophilic group such as a sulfo group or a carboxyl group.

Specific examples of ETA are shown below.

(X-1) (X-2) (X-5) (X-6) (X-7) (X-8) (X-3) (X-4) (X-9) (X-10) (X-11) (X (X 13) 15) (X 17) (X-12) (X-14) (X 16) The ETA precursor used in the present invention is is a compound that does not have a developing effect, but 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 has a reactive functional group blocked with a blocking group.
Although it does not function as an ETA before development, it can function as an ETA because the blocking group is cleaved under alkaline conditions or when heated.

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

The ETA precursor used in the present invention is a known compound, for example, US Pat. No. 767.704, US Pat.
, No. 967, No. 3,246,988, No. 3,29
No. 5,978, No. 3.462.266, No. 3,5
No. 86.506, No. 3,615,439, No. 3.
No. 650,749, No. 4.209,580, No. 4
, 330.617, British Patent No. 4,310,612, British Patent No. 1.023,701, British Patent No. 1.023,701, British Patent No. 1.023,701; 231°83
No. 0, No. 1,258,924, No. 1゜346.9
No. 20, JP-A-57-40245, JP-A No. 5B-1139
The developer precursors described in Japanese Patent No. 58-1140, Japanese Patent No. 59-178458, Japanese Japanese Patent No. 59-182449, and Japanese Japanese Patent No. 59-182450 can be used.

In particular, JP-A-59-178458, JP-A No. 59-18244
The precursors of 1-phenyl-3-pyrazolidinones described in No. 9 and No. 59-182450 are preferred.

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 or only to some emulsion layers.
Further, it can be added to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, protective layer, etc.), or even to all layers. 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 substance or in a separate layer; however, it is preferable that the diffusion-resistant electron donor be present in the same layer as the dye-donating substance. preferable,
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 dye to be used is 0.01 to 50 mol in total, preferably 0.91 to 50 mol, per 1 mol of the dye-donating substance.
5 moles, halogenated! Total amount is 0.0 per 11 r-le.
0.01 to 5 mol, preferably 0.01 to 1.5 mol.

Moreover, ETA is 60 mol% or less, preferably 40 mol% or less of the total reducing agent. When PTA is dissolved in water and supplied, the concentration of ETA is 1O-4 mol/l-1 mol/
l is preferred.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044. Yes! Two or more types of silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and am salt is 50cm to 10g/ in terms of W&.
rrf is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RD176
43 (I978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 59-168442, or mercapto compounds and their Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. Examples include those described on pages (26) to (28) of JP-A-62-253159.

Specifically, a transparent or translucent hydrophilic binder is preferred, and includes a protein compound such as gelatin, a gelatin derivative, or a natural compound such as a cellulose derivative, a starch, acacia, dextran, a polysaccharide such as pullulan, etc.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other high molecular weight compounds. In addition, super absorbent polymers described in JP-A-62-245260 etc., namely -COOM or -5O,M(
M is a hydrogen atom or an alkali metal) homopolymers of vinyl monomers or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium meracrylate, ammonium methacrylate, Sumitomo Chemical)
Sumikagel L-5H), manufactured by Co., Ltd., is also used. Two or more of these binders can also be used in combination.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly 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.

In the present invention, the amount of binder applied is 20
The amount is preferably 10 g or less, more preferably 7 g or less.

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain various polymers 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. It can contain latex. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40°C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used for the back layer, curling can be prevented. is obtained.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be introduced into the layers of the light-sensitive material by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154, JP-A-59-83154;
No. 178451, No. 59-178452, No. 59-1
No. 78453, No. 59-178454, No. 59-17
8455, No. 59-178457, etc., if necessary, with a boiling point of 50°C to 1°C.
It can be used in combination with a low boiling point organic solvent of 60°C.

Has a high boiling point! The amount of solvent depends on the dye-providing compound used.
10 g or less, preferably 5 g or less. Also, 1 cc or less, and even 0.0 cc or less per 1 g of binder.
5 cc or less, particularly 0.3 cc or less is suitable.

Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open 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, JP-A-59
-157636, pages (37) to (38), those listed as surfactants can be used.

In the present invention, the photosensitive material is simultaneously activated for development! Compounds that stabilize imitation can be used. For specific compounds preferably used, see U.S. Patent No. 4,50.
No. 0,626, columns 51-52.

By diffusion transfer of dye, i! In the system for forming imitations, a dye-fixing material is used together with a light-sensitive material.0 Even if the dye-fixing material is coated separately on a separate support from the light-sensitive material, it may be coated on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye-fixing material, which may be coated on the body, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Pat. No. 4.500.626, No. 57m. The relationships described are also applicable 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, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463.079 may 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.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 6 of JP-A-62-2-53159.
There are those described in Nos. 2 to 245253.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. For example,
Various modified silicone oils described in "Modified Silicone Oil J Technical Data P6-18B" published by Shin-Etsu Silicone,
In particular, carboxy-modified silicone (product name X-22-37)
10) etc. are effective.

Also, JP-A-62-215953 and JP-A No. 63-46449.
The silicone oil described in this issue is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Examples of the antifading agents include antioxidants, ultraviolet absorbers, and certain metal complexes.

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

Benzotriazole compounds (
U.S. Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,681, etc.),
Benzophenone compounds (JP-A-46-2784, etc.)
, Other Jikai No. 54-48535, No. 62-1366
There are compounds described in No. 41, No. 6188256, and the like.

Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
No. 4.245,018, columns 3 to 36, No. 4,25 of the same
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A No. 61-88256, pages (27) to (29), JP-A No. 63
-199248, Japanese Patent Application No. 62-234103, No. 6
There are compounds described in No. 2-230595 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
It is described on pages I25) to (I37).

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. .

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

A fluorescent brightener may be used in the light-sensitive material or the dye-fixing material. In particular, it is preferable to incorporate the fluorescent brightener into the dye-fixing material or to supply it from outside the light-sensitive material. ,VeenkatarasanWE rTh
e Chemistry of 5ynthetic
Dyes J Volume V Chapter 8, JP-A-61-143752
Examples include compounds described in No.

More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Examples include hardeners described in No. 1-18942 and the like. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-ethylene-bis(vinylsulfonylacetamide)ethane) etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Various surfactants can be used in the constituent layers of photosensitive materials and dye-fixing materials for the purposes of coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of agents are JP-A-62-173463 and JP-A No. 62-1.
It is described in No. 83457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
Typical examples of organic fluoro compounds that may be included for the purpose of preventing static electricity, improving peelability, etc. are Japanese Patent Publication No. 57-9053, columns 8 to 17, and Japanese Patent Application Laid-Open No. 1983-1989.
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described on page 29 of No. 6, patent applications No. 110064/1982 and No. 62-11 of benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. 0065.

In addition, thermal solvents, antifoaming agents, antibacterial agents, colloidal silica, etc. may be included in the constituent layers of the photosensitive materials and dye fixing materials. −
No. 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. The image formation accelerator can be used to promote the oxidation-reduction reaction between a silver salt oxidizing agent and a reducing agent, or from a dye-donating substance. It has functions such as promoting reactions such as generation of dyes, decomposition of dyes, and release of diffusible dyes, and promotion of transfer of dyes from the light-sensitive material layer to the dye fixing layer. It is classified into 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 multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
, No. 739, columns 38-40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amine a by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat.

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

In addition to the above, there are also sparingly soluble metal compounds described in European Patent Publication No. 210,660 and U.S. Pat. Combinations of compounds (referred to as ti-forming compounds) and compounds that generate bases by electrolysis as described in JP-A-61232451 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 acid 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.

The development stopper mentioned here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
32).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. -For boat fishing, paper and synthetic polymers (films) can be used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose 1! (for example, triacetyl cellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, mixed paper made from synthetic resin pulp such as polyethylene, and natural bulbs, Yankee paper,
Baryta paper, coachite paper (especially 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, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used.

The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as Alnasol or tin oxide, a carbon blank, or other antistatic agent.

Methods of exposing and recording images on photosensitive materials include, for example, using a camera to directly photograph wind or people, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which an original image is scanned and exposed through a slit using an exposure device, etc., a method in which a light-emitting diode, various lasers, etc. are emitted to emit iI copy information via an electrical signal, and Wi
There is a method of outputting the tracing information to an image display device such as a CRT, liquid crystal display, electroluminescence display, or plasma display, and exposing the image directly or through an optical system.

Light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. as mentioned above, such as U.S. Pat. No. 4,500.6.
The light source described in No. 26, column 56 can be used.

Further, 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, inorganic compounds such as BaBzOn, urea derivatives, nitroaniline derivatives, such as 3-methyl-
Nitropyridine-N-oxide derivatives such as 4-nitropyridine-N-oxide (POM), JP-A-61-5
Compounds described in No. 3462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal guided waveguide type, fiber type, etc. are known, and either of them is useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Network Signal Standard (NTSC), and images obtained by dividing an original picture into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for the diffusion transfer of the heated developer or dye.

In this case, the transparent or opaque heating element is
1-145544 and the like can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development process can be developed at about 0°C to about 250°C, but it is particularly useful to use a heating temperature of about 0°C to about 180°C.The dye diffusion transfer process is performed simultaneously with heat development. 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, the heating temperature in the transfer process is 50°C or higher. More preferably, the temperature is about 10° C. lower than the temperature in the development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 61-2380
56, 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 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters 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 of applying them to dye fixing materials, photosensitive materials, or both.

The amount used is a small amount, less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially in mass sales, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film). good.

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). It is also possible to use the solvent by incorporating it into the photosensitive material, the dye fixing material, or both in advance, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing material. The aqueous thermal solvent may be incorporated into either the photosensitive material or the dye fixing material.
It may be incorporated in both, and the layer to be incorporated may also be an emulsion layer,
Although it may be an intermediate layer, a protective layer, or a dye fixing layer, it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

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.

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

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention; for example, JP-A-59-75247;
Apparatuses described in Japanese Utility Model No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Implementation g41 A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and HO (CHz) in 800 cc of water)
)yo5(CHi) xs(CHz) 0.3g of tOH
(added and kept warm at 55℃), add the following solution (I) and (2)
) was added at the same time over a period of 30 minutes. Thereafter, the following solutions (3) and (4) were simultaneously added over 20 minutes. Further, after starting the addition of the liquid (3), the following dye solution was added over a period of 18 minutes from 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2, p, and Ag to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3
,3a,? - Optimal chemical sensitization was carried out by adding tetrazaindene and chloroauric acid. In this way, the average particle size, 0.
600 g of a 40 μm monodispersed tetradecahedral silver iodobromide emulsion was obtained.

Milk IL←U A well-stirred gelatin aqueous solution (Table 1) was kept warm at 50°C, and Table 2 (7) (+) solution and (II) solution were added over 30 minutes. I) solution and (IV) solution 3
The dye solution in Table 3 was added one minute after the addition was completed.

Table 1 The yield was 630g.

1 measurement" 0- A well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 6 ml of sodium chloride in 80 ml of water)
30g of the following chemical A and 301g of the following chemical A and kept at 50°C), add the following solutions (I) and (II) at the same time.
Addition was made at equal flow rates over a period of minutes. Then further below (I)
Solution and solution (IV) were added simultaneously over 30 minutes. Further, starting from 3 minutes after the start of addition of solutions (I[I) and (IV), the following dye solution was added over a period of 20 minutes.

After washing with water, desalting, treating with lime, adding 22 g of ossein gelatin to adjust the pH to 6.2 and PAg to 7.7, sodium thiosulfate and 4-hydroxy 6-methyl-1,3,
Add 3a,7-chitrazaindene and chloroauric acid to 60°
Optimal chemical sensitization was achieved with C. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.38 μm was obtained. Yield was 635g.

Table 2 Table 3 (Composition of dye solution) After washing with water and desalting, add 20 g of gelatin and adjust the pH and pAg to tJ.
Section 4: Triethyl urea, chloroauric acid, 4-hydroxy-
Optimal chemical sensitization was performed using 6-methyl-1,3,3a,7-chitrazaindene.

The resulting emulsion was a 0.40 μm monodispersed cubic emulsion CI.Dye solution: 67 g of dye (a) and 133 g of dye (b) below were dissolved in 100 g of methanol.

Pigments (a) Yellow, magenta, and cyan were each added to 50 cc of ethyl acetate according to the following formulations and dissolved by heating at about 60°C to form a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 cc of water were mixed with stirring, and then dispersed in a homogenizer for 10 minutes at LOOOORPM. This dispersion is called a gelatin dispersion of a dye-providing compound.

Dye-donating compound (2) Dye-donating compound (3) Electron donor ■ Dye-donating compound (I) High boiling point solvent ■ Electron transfer agent precursor ■ Next, we will describe how to make a dispersion of the electron donor for the intermediate layer. .

The following electron donor ■23.6g and the above high boiling point solvent ■8
．． 5 g was added to 30 cc of ethyl acetate to form a homogeneous solution.

This solution and 100 g of a lO% aqueous solution of lime-treated gelatin,
Sodium bisulfite 0. After stirring and mixing 25 g of sodium dodecylbenzenesulfonate, 0.3 g of sodium dodecylbenzenesulfonate, and 30 cc of water, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of electron donor (1).

Electron donor ■ 12.5 g of zinc hydroxide with an average particle size of 0.2 μ, carboxymethyl cellulose Ig as a dispersant, 0.1 g of sodium polyacrylate, and 100 g of 4% gelatin water Ig solution.
In addition to cc, the mixture was ground for 30 minutes in a mill using glass beads having an average particle size of 0.75 am.

The glass peas were separated to obtain a dispersion of zinc hydroxide.

5 of 1 ' 2.5 g of activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical, 1 g of Demol N manufactured by Kao Soap ■ as a dispersant, 0.25 g of polyethylene glycol nonylphenyl ether, and 10 g of a 5% gelatin aqueous solution.
In addition to 0 cc, the mixture was ground for 120 minutes using glass beads with an average particle size of 0.75 m in a mill. The glass beads were separated to obtain an activated carbon dispersion with an average particle size of 0.5 μm.

Add 10g of the electron transfer agent below, 0.5g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5g of the anionic surfactant below to 5% gelatin water. In addition to the 8 liquid, the mixture was ground for 60 minutes using glass peas with an average particle size of 0.75 mm. Separate the glass beads and reduce the average particle size to 0.
．． A 3μ electron transfer agent dispersion was obtained.

Electron transfer agent ■ Anionic surfactant CHzCOOCHzCH (CJs) CJwNaOsS
CHCOOCHzCH(CzHs)CaHw (7) Preparation of Comparative Photosensitive Material The material prepared as above is shown in Table 4.

A fully developed photosensitive material 1 having a multilayer structure was prepared.

Further, in the above photosensitive material I, an acetylene compound or
Photosensitive materials 2 to 6 were prepared by adding a nitrogen-containing heterocyclic compound having a mercapto group as shown in Table 5.

602- Note 6) Surfactant ■ In Photosensitive Material 1, the acetylene compound of the present invention and a nitrogen-containing heterocyclic compound having a mercapto group are added as shown in Table 5 to form Photosensitive Materials 7 to 1 Note 7). Electron transfer agent 1 was prepared.

Each layer was coated with the composition shown in Table 2 on a paper support laminated with polyethylene in an amount of .000 to produce a dye fixing material.

Note 8) as a child transfer agent Note 9) Hardening agent [phase] Bis(vinylsulfonylacetamide) Ethane silicone oil (I) CH3C83C1(j CH3-5i-0-←5i-0″f-rr-5i C
H3(CHx) l IC0OHCHx
(CHz) +□C0OH surfactant (I) Surfactant (2) Cs F , S Ox N CH! COOKC3H surfactant (3) CH3 surfactant (4) C,H.

C1hCOOCHzCHC-Hw NaOsS CHCOOCHgCHCaHqC*Hs Optical brightener (I) 2.5bis(5-tert-butylbenzoxazole(
2)) Thiophene surfactant (5) C,L C+F+tSOJ→CtlzCHzO+"÷CHr+r
SOaNa water-soluble polymer (I) Sumikagel L5-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant (I) High boiling point solvent (I) Hardener (I) Cloaking agent (I) 8 Silica mantle agent (2) 1 Benzoguanamine resin (average particle size 15 μm) B and G in which a tungsten light bulb is used in the above-mentioned multilayered color photosensitive material and the density changes continuously.

Exposure was made for 1/10 second at 4000 lux through R and gray color separation filters.

While feeding the exposed light-sensitive material at a linear speed of 20 .mu.sec., 15 d/rrf of water was supplied to the emulsion surface using a wire bar, and the material was immediately superimposed on the dye-fixing material so that the membrane surface was in contact with the material.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C.

Next, when the photosensitive material was peeled off from the dye fixing material, blue, green, red, and gray images were obtained on the dye fixing material corresponding to the B, G, R, and gray color separation filters.

The maximum density (Dmax) and sensitivity of each color of cyan, magenta, and yellow in the gray part were measured. These results are shown in Table 5.

From the results in Table 5, it is clear that the photosensitive material of the present invention, which contains a nitrogen-containing heterocyclic compound having a mercapto group in the photosensitive layer and an acetylene compound in the non-photosensitive layer, can produce images with high maximum density without impairing sensitivity. You can see what you can get.

Procedural amendment

Claims (1)

[Scope of Claims] A heat-developable 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. , at least one photosensitive layer contains a nitrogen-containing heterocyclic compound having a mercapto group, and at least one non-photosensitive layer contains one or more compounds represented by the following general formula (I). Development photosensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above general formula (I), L is a simple bond or
Represents a divalent linking group. n represents an integer from 1 to 4. n=
When 1, R_1 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. When n=2, 3 or 4, R_1 represents a divalent, trivalent or tetravalent residue, respectively. R_2 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 represents. When n is 2, 3 or 4, -L-C≡C-R_2 may be the same or different. However, this excludes the case where L is a simple bond and R_1 and R_2 are both hydrogen atoms when n=1.