JP2549549B2 - Heat developable color photosensitive material and image forming method using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heat-developable color light-sensitive material and an image forming method using the same.

(Background technology and its problems) Photothermographic materials are well known in this technical field, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-Silver Salt Photo Edition (1982, published by Corona Co., Ltd.). 242
Pp. 255, U.S. Pat. No. 4,500,626.

Many methods have been proposed for obtaining a positive color image by thermal development.

For example, in U.S. Pat.No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no dye releasing ability, is made to coexist with a reducing agent or a precursor thereof, and the reducing agent is oxidized by thermal development depending on the exposure amount of silver halide. Then, a method of releasing the diffusible dye by reducing with a reducing agent remaining without being oxidized has been proposed. Further, in European Patent Publication No. 220746 and Kokai Giho No. 87-6199 (Vol. 12, No. 22), NX bond (X is oxygen atom, nitrogen atom or A heat-developable color light-sensitive material using a non-diffusible compound which releases a diffusible dye by reductive cleavage of (representing a sulfur atom) is described.

However, it has been found that when the above-mentioned reducible dye-donating compound is used in combination with a reducing agent or its precursor in combination with a silver halide emulsion, the stain of the color image is high.

In order to suppress stain of the photothermographic material for positive image formation using such a reducible dye-donating compound, in addition to an electron donor which is a diffusion-resistant reducing agent as a reducing agent, a diffusible reducing agent is used. It is effective to use an electron transfer agent, which is an agent, but the generated electron transfer agent radicals diffuse into other layers having different color sensitivities and cross-oxidize the electron donors to reduce the image density. The color reproduction deteriorates. For this reason, it has been attempted to provide an intermediate layer between photosensitive layers having different color sensitivities or to contain a reducing substance in the intermediate layer (Japanese Patent Application No. 62-279842). In the case of such a heat development diffusion transfer type light-sensitive material, the amount of the binder in the intermediate layer and the amount of the reducing substance added are limited in terms of image forming speed, resolution, film quality and the like, and therefore further improvement is required.

Further, the light-sensitive material containing the above-mentioned diffusible reducing agent is apt to cause fog in silver halide during heat development, resulting in a decrease in density and an increase in minimum density (Dmin).
As measures against this, it has been proposed to add a development inhibitor (antifoggant) to the silver halide emulsion layer or to use a development inhibitor precursor (Japanese Patent Application No. 62-82284).
No. 62-310028).

However, in this case, the sensitivity is lowered and the photographic properties of the light-sensitive material are likely to change during raw storage, and further improvement is required.

(Object of the Invention) An object of the present invention is to increase the image density and improve the color reproducibility of a heat-developable color light-sensitive material using a reducible dye-donating compound.

(Constitution of the Invention) An object of the present invention is to provide a support, at least a light-sensitive silver halide, a binder, a diffusible reducing agent, and a diffusion-resistant reducible dye-donating compound which releases a diffusible dye when reduced. A heat-developable color light-sensitive material having at least two light-sensitive layers having different color sensitivities, and releasing a diffusion-resistant reducing agent and a diffusible development inhibitor between the two light-sensitive layers. Heat-developable color light-sensitive material having layers each containing at least one diffusion-resistant development inhibitor precursor which can be used, and a color image characterized by being heat-developed after or simultaneously with image exposure. Achieved by the forming method.

Examples of the development inhibitor precursor of the present invention include compounds represented by the following general formula [I] that release a development inhibitor upon reduction.

General formula [I] PWRTime _t AF In the formula, PWR represents a group that is reduced (releases Time _t AF. Time releases AF through a subsequent reaction triggered by reduction of PWR. Represents a group.

 t represents an integer of 0 or 1.

AF represents a group having an action of suppressing development after being released.

 First, PWR will be explained in detail.

PWR is U.S. Pat.No. 4,139,389, or U.S. Pat.
No. 379, No. 4,564,577, JP-A No. 59-185333, No. 57-8445.
As disclosed in No. 3, it corresponds to a portion 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. Good, U.S. Pat.No. 4,232,107,
JP-A-59-101649, Research Disclosure (198
4) As disclosed in IV, 24025 or JP-A-61-88257, an electron-accepting quinonoid center in a compound that releases a photographic reagent by an electron transfer reaction in the molecule after reduction and the quinoid center It may correspond to the portion containing the carbon atom connecting the reagent. Further, JP-A-56-142530, U.S. Patents 4,343,893 and 4,619,884.
, The aryl group substituted with an electron-withdrawing group in the compound that releases a photographic reagent after the single bond is cleaved after reduction, and the atom (sulfur atom, carbon atom, or nitrogen atom) connecting the aryl group and the photographic reagent. ) May be included. It may also correspond to a nitro group in a nitro compound which releases a photographic reagent after electron acceptance and a portion containing a carbon atom which connects the nitro group and the photographic reagent as disclosed in US Pat. No. 4,450,223. And corresponding to the dieminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance described in U.S. Pat.No. 4,609,610 and the moiety containing the carbon atom connecting it to the photographic reagent. Is also good.

In addition, SO ₂ -X is contained in one molecule described in Japanese Patent Application No. 62-106885.
(X represents any one of oxygen, sulfur and nitrogen) and a compound having an electron-withdrawing group, a PO-X bond (X is as defined above) in one molecule described in Japanese Patent Application No. 62-106895. the electron attractive group - a compound having an electron withdrawing group, C-X 'bond (X' a represents the X synonymous or -SO ₂₎ in one molecule described in Japanese Patent Application Sho 62-106887 And compounds having the same.

In addition, groups described in Japanese Patent Application Nos. 62-319989 and 62-320771, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used.

In order to more fully achieve the object of the present invention, among the compounds of general formula [I], those represented by general formula [I-1] are preferable.

General formula [I-1] (Time _t AF is combined with at least one of R ¹⁰¹ , R ^{102 and} EAG.

The part corresponding to PWR in the general formula [I-1] will be described.

X represents a group (-N (R ¹⁰³ )-) containing an oxygen atom (-O-), a sulfur atom (-S-) and a nitrogen atom.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent a group other than a hydrogen atom or a simple bond.

Examples of the group other than the hydrogen atom represented by R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, and a sulfamoyl group. These may have a substituent.

R ¹⁰¹ and R ¹⁰³ are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups,
An acyl group and a sulfonyl group are preferred. R ¹⁰¹ , and
The carbon number of R ¹⁰³ is preferably 1 to 40.

R ¹⁰² is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group described for R ¹⁰¹ and R ¹⁰³ . The carbon number is preferably 1-40.

R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ may combine with each other to form a 5- to 8-membered ring.

 Oxygen is particularly preferable as X.

 The EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula [I-
Among the compounds represented by 1], those represented by the general formula [I-2] are preferable.

General formula [I-2] (Time _t AF is bound to at least one of R ¹⁰⁴ and EAG.

 X has the same meaning as above.

R ¹⁰⁴ represents an atomic group which is bonded to X and a nitrogen atom to form a 5- to 8-membered monocyclic or condensed heterocycle including the nitrogen atom.

Examples of the ring formed by include the following, which are shown together with the position of EAG.

It is desirable that the precursors of this invention are themselves non-migratory in the photographic layer and, therefore, are EAG, R ¹⁰¹ , R ¹⁰² , R
It is desirable to have a ballast group having 8 or more carbon atoms at the ¹⁰⁴ or X position (particularly at the EAG position).

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

General formula [A] In the general formula [A], Z ₁ is Represents

V _n represents an atomic group forming a 3- to 8-membered aromatic with Z ₁ and Z ₂ , and n represents an integer of 3 to 8.

_{V 3; -Z 3 -, V} 4; -Z 3 -Z 4 -, V 5; -Z 3 -Z 4 -Z 5 -, V 6; -Z 3 -Z
_{4 -Z 5 -Z 6 -, V} 7; -Z 3 -Z 4 -Z 5 -Z 6 -Z 7 -, V 8; -Z 3 -Z 4 -Z 5 -Z 6 -Z
₇ -Z ₈ - it is.

Z _{2 to} Z ₈ are each It represents —O—, —S—, or —SO ₂ — and each Sub represents a simple bond (pi bond), a hydrogen atom or a substituent described below. Sub is the same,
Further, they may be different from each other, or may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocyclic or heterocyclic ring.

In the general formula [A], Sub is selected so that the sum of the Hammett substituent constants sigmapara of the substituents is +0.50 or more, more preferably +0.70 or more, and most preferably +0.85 or more.

EAG is preferably an aryl group substituted with at least one electron-withdrawing group, or a heterocyclic group. The substituent bonded to the aryl group or heterocyclic group of EAG can be used for controlling the physical properties of the entire compound. Examples of physical properties of the whole compound include, in addition to being able to adjust the ease of receiving electrons, for example, water solubility, oil solubility, diffusibility, sublimability, melting point, dispersibility in a binder such as gelatin, reactivity to a nucleophilic group, It can be used to adjust the reactivity to an electrophilic group.

Specific examples of EAG are described in European Patent Publication No. 220746A2 Nos. 6-7.
It is described on the page.

Time represents a group that releases AF through a subsequent reaction by using cleavage of the nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bond as a scratch.

Various groups represented by Time are publicly known, and for example, JP-A-61-61
-147244, pages (5) to (6), pages 61-236549, (8)-(14), and European Patent 220,746, pages 10 to 20.

As another development inhibitor precursor of the present invention, a photographically useful reagent precursor in a conventional photographic system which releases a development inhibitor by the action of a base may be used.
Of these, the following three types are preferable.

(Type 1)> C = C <group,> C = 0 group,> C = S group,> C = N group
And> C = N Have at least one of the groups
Bases or base precursors on the carbon atoms of the functional groups of
By the attack of the bases released from
A precursor compound that releases an image suppressor (hereinafter referred to as AF)
Stuff.

AF following base attack on the carbon atom of these functional groups
The type of emission is as follows: Emission by cleavage of bonds directly bonded to these carbons: Emission by cleavage of other bonds with electron transfer: Intramolecular nucleophilicity with or without electron transfer Release upon cleavage of other bond by attack: release consisting of a plurality of the above reaction forms: release via timing group, etc.

(Type 2) A precursor compound that releases AF by deprotonation by a base or a base released from a base precursor and subsequent reaction. The reaction mode of AF release in such a precursor compound is the same as that described in the above (Type 1).

(Type 3) A precursor compound having at least one of the following and releasing AF by attack of a base on the sulfur atom or phosphorus atom of these functional groups and subsequent reaction.

The reaction mode of AF release in such a precursor compound is the same as described in (Type 1) above. However, a direct electron transfer type on a sulfur atom or a phosphorus atom is not included.

A compound in which a hydrogen atom of the mercapto group of the development inhibitor having a mercapto group is replaced by a group having a functional group of (Type 1) to (Type 3) is particularly preferable as a development inhibitor precursor.

Specific examples of the precursor compound belonging to (Type 1) include JP-B-48-9968, JP-A-52-8828, and JP-A-52-8828.
57-82834, U.S. Pat.Nos. 3,311,474, 3,615,617, etc., sulfur release type antifoggants, development inhibitor precursors: Japanese Patent Publication No. 54-39727, U.S. Pat.
No. 478, No. 3,932,480, No. 3,993,661, JP-A-58-
1140, 58-209736, 59-225168, etc. Precursors that release AF by cleavage of the acetyl group and subsequent electron transfer or further decarboxylation: JP-B-57
-22099, U.S. Pat. No. 4,199,354, and precursors that release AF by ring cleavage and subsequent intramolecular ring closure reaction described in JP-A-55-53330: JP-A-55-53330 Precursor releasing AF by hydrolysis and subsequent intramolecular ring closure reaction: JP-A-57-76541 and 59
-135949, 57-179842, 59-3434, 59-137945
No. 59-140445, etc., a precursor that releases AF with ring cleavage followed by electron transfer and decarboxylation: Research Disclosure 15,162 (1976).
), JP-A-56-77842, U.S. Pat.No. 4,307,175, etc., and a precursor which releases AF by nucleophilic attack of a base on a carbon-carbon double bond and subsequent elimination. it can.

Specific examples of the precursor compound belonging to (Type 2) include, for example, Japanese Patent Publication No. 55-34927, U.S. Pat. No. 4,009,029,
JP-B-55-9696, JP-B-55-17369, JP-A-59-105640,
59-105641, 59-105642, etc., a precursor that releases AF by utilizing the so-called reverse Michael reaction: JP-B-54-39727, JP-A-57-135944, 57-135945, same
57-136640, 58-976, 58-1139, etc.> N
-H or -OH dissociates to generate anions, and intramolecular electron transfer causes the formation of quinonemethide-like compounds, which causes AF
Precursors that release ## STR3 ## include the method of utilizing the ring opening of benzisoxazole to o-cyanophenol described in JP-A-59-202459.

As the precursor compound belonging to (Type 3),
For example, a sulfonyl group-containing precursor compound described in JP-A-52-8828 can be mentioned.

In the present invention, the development inhibitor precursor represented by the following general formula [II] or [III] is particularly preferable.

General formula (II) In the above general formula [II], R ⁵ and R ⁶ may be the same or different and each is a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group or nitrogen-containing heterocycle. Represents a group, preferably a substituted or unsubstituted aryl group or nitrogen-containing heterocyclic group.

Examples of the substituent in this case include an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an amino group and N.
-Substituted amino group, acylamino group, carbamoyl group, N
-Substituted carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, N-substituted sulfamoyl group, cyano group, nitro group, halogen atom and the like.

Among these, preferable substituents are an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a sulfonylamino group and a halogen atom.

L represents a single bond or a substituted or unsubstituted divalent group, p and q are 1 or 2, respectively, and n
Is 0 or 1.

The divalent group represented by L in the general formula [II] is preferably an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S -, - SO -, - SO 2 -, A divalent group represented by or a combination of a plurality of these divalent groups is preferable.

Here, R ⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), an aryl group having 6 to 10 carbon atoms (eg, phenyl group, etc.) Or an aralkyl group having 7 to 10 carbon atoms (eg, benzyl group). When L is not a single bond, these divalent groups may be further substituted, and examples of the substituent in this case include an alkyl group and an aryl group.

General formula (III) In the above general formula [III], R ⁵ and R ⁶ are each represented by the general formula [I
It is synonymous with I]. R ⁸ and R ⁹ may be the same or different and each is a hydrogen atom or a carbon number of 1 to 4.
Represents an alkyl group. Each of a and b is an integer of 0 to 3 and may be the same or different. X ¹ and X ² may be the same or different and each represents an ester bond, a substituted or unsubstituted amide bond or an ether bond. L'represents an alkylene group, a phenylene group or a xylylene group. Further, when X ¹ or X ² is an amide group, the substituents on the nitrogen may be bonded to each other to form a heterocycle together with L ′ and a part of each of X ¹ and X ² . n and m are each an integer of 0 or 1.

Examples of the alkyl group for R ⁸ and R ⁹ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. R ⁸ , R
⁹ is preferably a hydrogen atom or a methyl group.

When X ¹ and X ² are an amide group, examples of the substituent include an alkyl group, an aryl group, etc., and the heterocycle composed of L ′ and a part of each of X ¹ and X ² is substituted. Also, as the hetero ring, for example, a perhydrotriazine ring,
Examples thereof include an imidazoline ring, a piperazine ring, a perhydropyrimidine ring and the like, and in particular, a perhydrotriazine ring can be substituted. As the substituent in this case, (Here, R ⁵ , R ⁸ and a are as defined above) and the like.

L'is preferably an alkylene group having 1 to 6 carbon atoms (for example, methylene group, ethylene group, trimethylene group, hexamethylene group, etc.), phenylene group or xylylene group.

X ¹ and X ² are preferably an amide bond or an ether bond.

As another development inhibitor precursor of the present invention, a compound (DIR compound) represented by the following general formula [IV], which releases a development inhibitor upon being oxidized, can be mentioned.

General Formula [IV] ATime _t AF In the formula, A is a redox mother nucleus that makes it possible to release Time _t AF by being oxidized. Time,
The definitions of t and AF are the same as in the general formula [I].

A of the general formula [IV] will be described in more detail. Examples of the redox nucleus represented by A include hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,2-naphthalene diol, 1,4-naphthalene diol, 1,6-naphthalene diol, 1,2 -Aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol and the like. At this time, the amino group has 1 to 25 carbon atoms
Is preferably substituted with a sulfonyl group or an acyl group having 1 to 25 carbon atoms. Examples of the sulfonyl group include a substituted or unsubstituted aliphatic sulfonyl group and an aromatic sulfonyl group. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of the protecting group are those having 1 to 25 carbon atoms, such as an acyl group, an alkoxycarbonyl group, a carbamoyl group, and further JP-A-59-197037 and JP-A-59-20.
The protecting group described in No. 1057 can be mentioned. Further, when possible, this protecting group may be bonded to a substituent of A described below to form a 5-, 6- or 7-membered ring.

The redox nucleus represented by A may be substituted at an appropriate position with an appropriate substituent. Examples of these substituents include those having 25 or less carbon atoms, such as an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amino group, a hydroxy group, an acyloxy group, an amide group, and a sulfonamide. Group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, or Time
_t AF etc. These substituents may be further substituted with the above-mentioned substituents. If possible, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol,
4-naphthalenediol, 1,4-aminonaphthol and the like. A is more preferably hydroquinone,
Catechol, p-aminophenol and o-aminophenol are exemplified. A is most preferably hydroquinone.

Preferred specific examples of A in the general formula [IV] are shown below. In addition, (*) in each structural formula shows the position where Time _t AF bonds.

15 carbon atoms as a diffusible development inhibitor represented by AF
Hereinafter, preferably 10 or less compounds, compounds having a mercapto group bonded to the heterocycle, for example, substituted or unsubstituted mercaptoazoles (specifically 1-phenyl-5-mercaptotetrazole, 1- (4-carboxy Phenyl) -5-mercaptotetrazole, 1- (3-
Hydroxyphenyl) -5-mercaptotetrazole,
1- (4-sulfophenyl) -5-mercaptotetrazole, 1- (3-sulfophenyl) -5-mercaptotetrazole, 1- (4-sulfamoylphenyl) -5
-Mercaptotetrazole, 1- (3-hexanoylaminophenyl) -5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1- (2-carboxyethyl) -5-mercaptotetrazole, 2-methylthio-5-mercapto -1,3,4-thiadiazole, 2
-(2-Carboxyethylthio) -5-mercapto-1,
3,4-thiadiazole, 3-methyl-4-phenyl-5
-Mercapto-1,2,4-triazole, 2- (2-dimethylaminoethylthio) -5-mercapto-1,3,4-thiadiazole, 1- (4-n-hexylcarbamoylphenyl) -2-mercaptoimidazole , 3-acetylamino-4-methyl-5-mercapto-1,2,4-triazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-6-nitro-1, 3-Benzoxazole, 1- (1-naphthyl) -5-mercaptotetrazole, 2-phenyl-5-mercapto-1,3,4-
Oxadiazole, 1- {3- (3-methylureido)
Phenyl} -5-mercaptotetrazole, 1- (4-
Nitrophenyl) -5-mercaptotetrazole, 5-
(2-ethylhexanoylamino) -2-mercaptobenzimidazole, etc., and substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaine Den, 6-methyl-
2-benzyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6-phenyl-4-mercapto-1,3,3a, 7-tetrazaindene, 4,6-dimethyl-2-mercapto- 1,
3,3a, 7-Tetrazaindene, etc., and substituted or unsubstituted mercaptopyrimidines (specifically 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-propyl) Such as pyrimidine). Heterocyclic compounds capable of forming imino silver, such as substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6
-Dichlorobenzotriazole, 5-bromobenzotriazole, 5-methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6-dimethylbenzotriazole , 4,5,6,7-tetrachlorobenzotriazole, etc.), substituted or unsubstituted indazoles (specifically, indazole, 5-
Nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, 3-cyanoindazole, 3-n-butylcarbamoylindazole, 5-nitro-3-methanesulfonylindazole, etc.), substituted or unsubstituted benzimidazoles (In particular,
5-nitrobenzimidazole, 4-nitrobenzimidazole, 5,6-dichlorobenzimidazole, 5-cyano-6-chlorobenzimidazole, 5-trifluoromethyl-6-chlorobenzimidazole, etc.) and the like.

Specifically, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) 5-mercaptotetrazole, 1- (3-maleimidophenyl) 5-mercaptotetrazole, 5- ( Phenoxycarbonyl) benzotriazole, 5- (p-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethimethio-5-mercapto-1,3,4-thiadiazole,
5-nitro-3-phenoxycarbonylindazole,
5-phenoxycarbonyl-2-mercaptobenzimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5- (butylcarbamoylmethoxycarbonyl) benzotriazole, 5- (butoxy Carbonylmethoxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole,
1- {4- (2-chloroethoxycarbonyl) phenyl} -2-mercaptoimidazole, 2- [3- {thiophen-2-ylcarbonyl} propyl] thio-5-mercapto-1,3,4-thiadiazole, 5 -Cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto-1,3,4-oxadi Azole, 3- {4- (benzo-1,2-isothiazole-3-oxo-1,1-dioxy-2-yl) phenyl} -5-mercapto-4-methyl-1,2,4-triazole, 6-phenoxycarbonyl-2-mercaptobenzoxazole and the like can be mentioned.

These development inhibitors are those that bring about development inhibition (-SH
Via the S atom, the N atom of the imino group, etc.) of the precursor body. Particularly preferred development inhibitor precursors are compounds capable of releasing a development inhibitor having a mercapto group. Further, the development inhibitor precursor of the present invention has a carbon number of 16 or more, preferably 20 or more because it is diffusion resistant, or has a solubility in water at 25 ° C. of 0.
One or less, preferably 0.01 or less is desirable.

Specific examples of the development inhibitor precursor of the present invention are shown below, but the invention is not limited thereto.

The synthesis of the development inhibitor precursor used in the present invention is described in JP-B Nos. 47-44805, 54-17369, 55-9696 and 55-34.
927, 54-39727, JP-A-57-135944, 57-13594
No. 5, 57-136640, 55-53330, 57-76541, 57
57-135949, 57-179842, 62-215270, 61-67
No. 851, No. 61-124941, No. 61-147249, No. 61-185743
No. 61, No. 61-184539, No. 61-147244, No. 61-188540,
61-182039, 61-185744, 61-236548, 61-
267045, 61-267041, 61-269147, 61-26914
No. 3, No. 61-269148, No. 61-269147, Japanese Patent Application No. 62-310028
Can be easily synthesized according to the method described in No.

The amount of the development inhibitor precursor used in the present invention varies depending on the compound and the system used, but is 0.001 to 5 mmol, preferably 0.01 to 0.5 mmol per 1 m ² of the support in each intermediate layer, 0.001 per mol of diffusion resistant reducing agent in each intermediate layer
It is 5 to 10 mol, preferably 0.01 to 1 mol.

In the present invention, the development inhibitor precursor may be added to the emulsion layer, the color material layer, the protective layer, etc., if necessary.

As the diffusion resistant reducing agent used in the intermediate layer of the present invention, the compounds described in the following patents can be used.

U.S. Pat.Nos. 2,360,290, 2,403,721, 2,418,618
No., No. 2,701,197, No. 2,728,659, No. 2,735,765,
No. 2,732,300, No. 3,700,453, Japanese Patent Publication No. 59-37497, No.
56-21145, 51-12250, JP-A-59-202465, 55-
72158, 55-43521, 57-22237, 58-156932
No. 59-5247, No. 62-103638, West German patent publication (OL
S) 2,732,971, Japanese Patent Application No. 62-279842, 63-197566, etc.

Preferred are compounds represented by the following general formulas (V) to (VI).

General formula (V) General formula (VI) In the formula, X ¹¹ represents a hydroxyl group, —NR ¹⁵ R ¹⁶ or —NHSO ₂ R ¹⁷ .

R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen atoms; halogen atoms (eg, chlorine atom, bromine atom, etc.); aliphatic groups {eg, alkyl groups having 1 to 22 carbon atoms (eg, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group,
n-decyl group, tert-decyl group, n-dodecyl group, sec
-Dodecyl group, tert-dodecyl group, n-pentadecyl group, sec-pentadecyl group, tert-pentadecyl group, sec
-Octadecyl group, linear or branched alkyl group such as tert-octadecyl group), substituted alkyl group having 1 to 22 carbon atoms [as a substituent, a halogen atom, a hydroxyl group, an alkoxy group, a substituted amino group (alkyl or aryl group) Famoyl group and alkyl or arylcarbamoyl group), cyano group, 2
-Hydroxyethyl group, 3-methoxypropyl group, 3-
n-butylsulfamoylpropyl group)], C3-C22 alkenyl group (eg, allyl group), C5-C12 cycloalkyl group (eg, cyclohexyl group), C7-C22 aralkyl Group (eg, benzyl group, phenethyl group, 4-methylphenylethyl group, etc.)}; aryl group (eg, phenyl group or hydroxy group, alkyl group, alkoxy group, phenyl group substituted with arylsulfonyl group, etc.); alkoxy group, For example, an optionally substituted alkoxy group having 1 to 22 carbon atoms (eg, methoxy group, ethoxy group, n-
Butoxy group, n-dodecyloxy group and the like); aryloxy group, for example, aryloxy group having 6 to 22 carbon atoms which may be substituted (for example, phenoxy group, 4-n
-Butoxyphenyloxy group, etc.); an alkylthio group, for example, an alkylthio group having 1 to 22 carbon atoms which may be substituted (e.g., methylthio group, ethylthio group, n-pentylthio group, n-dodecylthio group, n-pentadecylthio group, 5-chloropentylthio group, etc.); Arylthio group, for example, arylthio group having 6 to 22 carbon atoms which may be substituted (eg, phenylthio group, 4-nitrophenylthio group, etc.); Sulfonyl group, for example, 1 to 30 carbon atoms An alkyl or arylsulfonyl group (eg, n-dodecylsulfonyl group); an acyl group, eg, an acyl group having 2 to 30 carbon atoms (eg, stearoyl group); a carbamoyl group, eg, a carbamoyl group having 2 to 30 carbon atoms (eg, 2,5-di-t-amylphenoxyethylcarbamoyl group); ester group, for example, 2 ~ 30 ester groups (eg p-
(T-octyl) benzyloxycarbonyl group); sulfamoyl group, for example, sulfamoyl group having 1 to 30 carbon atoms (eg octadecylsulfamoyl group, etc.); amide group, for example, amide group having 2 to 22 carbon atoms which may be substituted. (For example, acetamide group, benzoylamino group,
α- (2,4-di-t-amylphenoxy) butanamide group); a ureido group, for example, an optionally substituted ureido group having 1 to 22 carbon atoms (for example, N, N-diethylureido group); urethane A group such as an optionally substituted urethane group having 2 to 22 carbon atoms (for example, a phenoxycarbonylamino group, a butoxycarbonylamino group, etc.); a sulfo group; a carboxyl group, etc.

R ¹⁵ and R ¹⁶ represent a hydrogen atom, an aliphatic group, or an aryl group (the aliphatic group and the aryl group have the same definition as in R ^{11 to} R ¹⁴ ).

R ¹⁷ is an aliphatic group (for example, an alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-
Butyl group, n-octyl group, n-decyl group, n-dodecyl group, i-pentyl group and other linear and branched alkyl groups), substituted alkyl groups having 1 to 22 carbon atoms [halogen atom (chlorine as a substituent Atom or bromine atom) such as 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 4-bromobutyl group, dichloromethyl group, etc .; those having a hydroxy group such as 2-hydroxyethyl, 3- Hydroxypropyl group, 4-hydroxybutyl group, 6-hydroxyhexyl group, etc .; those having a sulfonyl group, such as ethanesulfonylmethyl group, n-butylsulfonylethyl group, arylsulfonylbutyl group, etc .; alkoxy group (eg, methoxy group, ethoxy group Base,
those having (n-butoxy group, n-oxyloxy group, etc.), for example, methoxymethyl group, methoxyethyl group, ethoxyethyl group, n-butoxyethyl group, 3-methoxypropyl group, n-hexyloxyethyl group, etc .; alkylthio Those having a group (eg, methylthio group, ethylthio group, n-hexylthio group, etc.), such as methylthiomethyl group, methylthioethyl group, 3-ethylthiopropyl group,
n-hexylthioethyl group or the like; or those having a substituted amino group, for example, 4- (N, N-dimethylamino) butyl group, 5-acetamidopentyl group, 4-methylsulfonylaminobutyl group, anilinomethyl group, etc.], cyclo Alkyl group (eg cyclohexyl), for example, aralkyl group having 7 to 22 carbon atoms and optionally having a substituent (eg benzyl group, 4-methylbenzyl group, 4-chlorobenzyl group, phenethyl group, 4-methylphenylethyl group) Group)}, a substituted amino group {for example, an amino group mono- or di-substituted with an alkyl group or an aryl group having 1 to 20 carbon atoms (such as a dipropylamino group)}, or an aryl group such as a phenyl group and a substituted phenyl group Group {having a halogen atom (eg, chlorine atom, bromine atom) as a substituent, for example, 4-chlorophenyl group Group, 4
-Bromophenyl group, 2-chlorophenyl group, etc .; those having a hydroxy group, for example, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2,5-dihydroxyphenyl group, etc .; those having an optionally substituted alkyl group, For example, 4-methylphenyl group, 4-i-propylphenyl group, 4-n-dodecylphenyl group, 2-chloro-
4-methylphenyl group, 4-chloromethylphenyl group,
2,5-dihydroxy-4-alkylphenyl group and the like; those having an alkoxy group which may be substituted, such as 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-n-
Propoxyphenyl group, 2-methyl-4-methoxyphenyl group, 3-methoxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-dodecyloxyphenyl group,
3-n-pentadecyloxyphenyl group and the like; those having an alkylthio group which may be substituted, for example, 4-methylthiophenyl group, 4-ethylthiophenyl group, 4-n-
Butylthiophenyl group, 3-n-hexylthiophenyl group, 3-n-decylthiophenyl group, etc .; those having an alkoxycarbonyl group, such as 4-methoxycarbonylphenyl group, 4-ethoxycarbonyl-2-chlorophenyl group, etc .; Those having a carboxy group, such as 4-carboxyphenyl group; those having a carbamoyl group, such as 4-carbamoylphenyl group, 4-methylaminocarbonylphenyl group, 2-chloro-4- (N, N-diethylaminocarbonyl) phenyl Group, etc .; substituted amino group (substituent may be further substituted, such as alkyl group, aralkyl group, phenyl group, acyl group derived from carboxylic acid or sulfonic acid)
With, for example, 4-methylaminophenyl group, 4-
(N, N-diethylamino) phenyl group, 4- (N-ethyl-N-benzylamino) phenyl group, 4-acetamidophenyl group, 4-methanesulfonylaminophenyl group, 3-n-heptanoylaminophenyl group, 3 -Phenylsulfonylaminophenyl group and the like; those having a nitro group, for example, 4-nitrophenyl group, 4-nitro-2-
Methylphenyl group, 2-chloro-4-nitrophenyl group, etc .; those having a cyano group, such as 4-cyanophenyl group, etc .; those having an acyl group, such as 4-acetylphenyl group, 2-methyl-4-acetylphenyl Group, 4-benzoylphenyl group and the like; those having a sulfonyl group, for example, 4-methanesulfonylphenyl group, 2-chloro-4
-Ethanesulfonylphenyl group, 4-phenylsulfonylphenyl group, 3- (2,5-dihydroxy-4-tert-
Pentylphenyl) sulfonylphenyl group and the like; those having a sulfamoyl group, for example, 3-sulfamoylphenyl group, 3- (n-butylaminosulfonyl) phenyl group, 2-chloro-4-phenylaminosulfonylphenyl group, etc .; Sulfo group Those having, for example, 4-sulfophenyl group, 2-chloro-5-sulfophenyl group, etc.} are represented.

R ¹⁸ represents an aryl group (the details of the aryl group are the same as R ¹⁷ ).

X ¹² , X ¹³ and X ^{14 each} represent a group selected from the same groups as X ¹¹ or a group selected from the same groups as R ^11, and at least one of X ¹² and X ¹⁴ is selected from the same group as X ^11. Represents a group represented by When both X ¹² and X ¹⁴ are groups selected from the same groups as X ¹¹ , X ¹³ represents a group selected from the same groups as R ¹¹ .

R ¹¹ and R ¹² , R ¹² and X ¹⁴ may together form a condensed ring, and R ¹⁵ and R ¹⁶ may together form a heterocycle.

The compounds represented by the general formulas (V) to (VI) are represented by R ^{11 to} R ¹⁸ in the compound in order to make the compound itself resistant to diffusion.
The total carbon number of X ^{11 to} X ¹⁴ is preferably at least 8 or more, more preferably 10 or more, and further preferably 15 or more. As another means for making the compound resistant to diffusion, the compounds of the general formulas (V) to (VI) may form a bis body or a tris body linked by any one of R ^{11 to} R ¹⁸ , or R ¹¹ It may be an oligomer or a polymer linked to a polymer by any one of to R ¹⁸ .

Among the general formulas (V) to (VI), the general formula (V) is particularly preferable.

In the general formula (V), preferred as X ¹¹ are a hydroxyl group and
It is an NHSO ₂ R ¹⁷ group, and particularly preferably a hydroxyl group.

In formula (V), preferably when X ¹³ is a group selected from the same group as R ^11, further X ^12, X ¹³ is a group selected from the same group as R ¹¹ X ¹⁴ is X A group selected from the same group as ¹¹ is particularly preferable.

Specific examples of the diffusion-resistant reducing agent are shown below, but the present invention is not limited to these compounds.

Regarding the synthesis method of the diffusion resistant reducing agent used in the present invention,
The method described in said patent can be used.

The amount of the reducing agent of the present invention added in each intermediate layer is
The amount is 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol per 1 m ^{2 of the} support, and 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol per 1 g of the binder in each intermediate layer. The reducing substance of the present invention can be added to the protective layer, if necessary.
When added to the protective layer, the amount added is 1 g of binder in the protective layer
It is 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol.

When there are a plurality of intermediate layers in the present invention, the development inhibitor precursor and / or the diffusion resistant reducing agent added to each intermediate layer may be the same or different, and a plurality of compounds may be used in combination. .

The photothermographic material of the present invention basically has a photosensitive silver halide, a reducible dye-donating compound, and a binder on a support, and further contains an organometallic salt oxidizing agent and the like as necessary. Can be made. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but it may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. For example, blue sensitive layer, green sensitive layer,
There are a combination of three layers of a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photothermographic material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer.

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 may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of the silver halide grains may be cubic, octahedron, tetrahedron, tabular with a high aspect ratio, or the like. In particular,
U.S. Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 1702
9 (1978), any of the silver halide emulsions described in JP-A-62-253159, etc. can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

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

Organic compounds that can be used to form the above organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. 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 described in JP-A-61-249044. Two or more kinds of organic silver salts may be used in combination.

The above-mentioned organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, RD17643
(1978) azoles and azaindenes described on pages 24 to 25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636. Salts, acetylene compounds described in JP-A-62-87957 and the like are used.

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

Specifically, U.S. Pat.No.4,617,257, JP-A-59-1805
No. 50, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for the purpose of supersensitization.

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

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

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing material. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal or a copolymer of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L manufactured by Sumitomo Chemical Co., Ltd.). -5H) is also used. These binders can be used in combination of two or more.

When employing a system in which a small amount of water is supplied for thermal development, the use of the superabsorbent polymer makes it possible to quickly absorb water. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer.

In the present invention, the coating amount of the binder is 20 g per 1 m ^2.
The amount is preferably the following, particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material include various polymers for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. A latex can be included. Specifically, JP-A-62-245258, JP-A-62-136648, and JP-A-62-1
Any of the polymer latices described in 10066 and the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C or lower) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl-preventing effect is obtained. can get.

The diffusible reducing agent used in the present invention is a compound having the ability to develop silver halide and capable of moving between coating layers. As a diffusible reducing agent, a compound (color developing agent) that develops silver halide to form an oxidant, and this oxidant undergoes a coupling reaction with a dye-donor compound, or the oxidant directly or electron-exchanges the dye-donor compound. Any compound (electron transfer agent) that cross-oxidizes via a diffusion-resistant reducing agent called a donor can be used. Examples of useful reducing agents include dihydroxybenzenes, catechols, pyrogallols, 3-pyrazolidones, p-phenylenediamines, p-aminophenols, sulfonamidephenols, and hydrazones. Specific examples thereof include: U.S. Pat.No. 4,500,62
No. 6 columns 49-50, No. 4,483, 914 columns 30-31, No. 4
4,330,617, 4,590,152, JP-A-60-140335, pages (17) to (18), 57-40245, 56-138736,
59-178458, 59-53831, 59-182449, 59-1
82450, 60-119555, 60-128436 to 60-1284
No. 39, No. 60-198540, No. 60-181742, No. 61-25925
No. 3, No. 62-244044, No. 62-131253 to No. 62-131256, and reducing agents and reducing agent precursors described in European Patent No. 220,746A2, pages 78 to 96, and the like.

A particularly preferred diffusible reducing agent is represented by the following general formula [XI]
Alternatively, it is a compound represented by [X-II].

In the formula, R'represents an aryl group. R ³¹ , R ³² , R ³³ , R
³⁴ , R ³⁵ and R ³⁶ represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group or an aryl group, and these may be the same or different.

Examples of the aryl group represented by R'in the general formulas [X-1] and [X-II] include a phenyl group, a naphthyl group, a tolyl group and a xylyl group. These groups may be substituted. For example, halogen atom (chlorine atom, bromine atom, etc.), amino group, alkoxy group, aryloxy group, hydroxyl group, aryl group, carbonamide group, sulfonamide group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyl Oxy group, carbonate group, carboxyl group, sulfo group,
It may be an aryl group substituted with an alkyl group (methyl group, ethyl group, propyl group, etc.).

R < ^{31 >} , R ^{< 32>} , R ^<33> , R ^<34 > of the general formulas [X-1] and [X-II],
The alkyl group represented by R ³⁵ and R ³⁶ has 1 to 10 carbon atoms.
Is an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), and these alkyl groups may be substituted with a hydroxyl group, an amino group, a sulfo group, a carboxyl group or the like. Further, as the aryl group,
A phenyl group, a naphthyl group, a xylyl group, a tolyl group or the like can be used. These aryl groups include halogen atoms (chlorine atom, bromine atom, etc.), alkyl groups (methyl group,
It may be substituted with an ethyl group, a propyl group, etc.), a hydroxyl group, an alkoxy group (a methoxy group, an ethoxy group, etc.), a sulfo group, a carboxyl group and the like.

In the present invention, the compound represented by the general formula [X-II] is particularly effective.

In the general formula [X-II], R ³¹ , R ³² , R ³³ and R
³⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 carbon atom
~ 10 substituted alkyl group, and a substituted or unsubstituted aryl group is preferable, more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group or a hydroxyl group,
It is a phenyl group substituted with a hydrophilic group such as an alkoxy group, a sulfo group and a carboxyl group.

Specific examples of the compound represented by the general formula [X-II] are shown below.

The compound of the present invention is also useful in a light-sensitive material containing a diffusible reducing agent precursor.

A diffusible reducing agent precursor does not have a developing action during the storage of the light-sensitive material before use, but is reduced only by the action of an appropriate activator (eg base, nucleophile, etc.) or heating. A compound that can release an agent.

Particularly, the diffusible reducing agent precursor used in the present invention does not have a function as a reducing agent before development because the reactive functional group of the reducing agent is blocked by a blocking group.
Since the blocking group is cleaved under alkaline conditions or when heated, it can function as a reducing agent.

Examples of the diffusible reducing agent precursor used in the present invention include 2 and 3-acyl derivatives of 1-phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxyalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium, etc.). , Calcium, barium, etc.), acyl halide derivatives of hydroquinone, oxazine and bisoxazine derivatives of hydroquinone, lactone type electron transfer agent (ETA) precursor, hydroquinone precursor having a quaternary ammonium group, cyclohexakis-2-ene −
In addition to 1,4-dione type compounds, compounds that release reducing agents through electron transfer reactions, compounds that release reducing agents through intramolecular nucleophilic substitution reactions, reducing agent precursors blocked with phthalide groups, and indomethyl groups Examples thereof include blocked reducing agent precursors.

The diffusible reducing agent precursor used in the present invention is a known compound, for example, U.S. Patent Nos. 3,241,967 and 3,246,9.
No. 88, No. 3,295,978, No. 3,462,266, No. 3,586,
No. 506, No. 3,615,439, No. 3,650,749, No. 4,209,5
No. 80, No. 4,330,617, No. 4,310,612, British patent No.
1,023,701, 1,231,830, 1,258,924, 1,346,920, JP-A-57-40245, 58-1139, 58
-1140, 59-178458, 59-182449, 59-182450
The developing agent precursors described in JP-A No. 1994-154 can be used.

In particular, JP-A-59-178458, JP-A-59-182449, JP-A-59-18245
Preferred are precursors of 1-phenyl-3-pyrazolidinones described in No. 0 and the like.

The amount of the diffusible reducing agent and / or the diffusible reducing agent precursor used has a wide range, but is preferably 0.001 mol to 5 mol, more preferably 0.01 mol to 1 mol of silver halide.
It is 1.5 mol.

As described above, in the present invention, a diffusion resistant reducing agent called an electron donor may be used in combination with the diffusing reducing agent. The electron donor is preferably used in close proximity to the dye-donor compound and is therefore used in the additive layer of the dye-donor compound. More preferably, it is used in the same layer as the dye-donor compound. Electron donors each having a diffusion resistant group, dihydroxybenzenes, catechols, pyrogallols, sulfonamide phenols, sulfonamide naphthols and the like European Patent Publication No. 220,746 page 84-95
Examples thereof include reducing agents and / or precursors thereof described in Japanese Patent Application Nos. 62-97880 and 62-301887. A compound of the same kind as the compound represented by the general formula (V) or (VI) of the present invention may be used as an electron donor.

Hydrophobic additives such as dye-donating compounds and electron donors can be introduced into the layer of the light-sensitive material by a method similar to the method for dispersing the compound of the present invention.

Examples of the reducible dye-donating compound used in the present invention include compounds represented by the following general formula [C].

General formula [C] PWRTime _t Dye Here, PWR, Time, and t are synonymous with general formula [I] (including a preferable example), and Dye represents a dye or a dye precursor.

The dyes represented by Dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes,
Examples include nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. Note that these dyes can also be used in the form of a temporarily shortened wave that can restore the color during development.

Typical specific examples of the reducible dye-donating compound used in the present invention are listed below, but the present invention is not limited to these, and European Patent Publication 220746A2, Publication Technical Report 87-6.
Dye-donating compounds described in 199 and the like can also be used.

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

The amount of the dye-providing compound used depends on the extinction coefficient of the dye, but is in the range of 0.05 to 5 mmol / m ² , preferably 0.1 to 3 mmol / m ² . The dye-providing substance can be used alone or in combination of two or more kinds. Further, in order to obtain an image of black or a different hue, as described in JP-A-60-162251, for example, at least one of cyan, magenta and yellow dye-providing substances in a layer containing silver halide or Two or more dye-donating substances that release a mobile dye having a different hue, such as a mixture contained in an adjacent layer, can also be used.

Hydrophobic additives such as dye-donor compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154, JP-A-59-178451, JP-A-59-17
8452, 59-178453, 59-178454, 59-178455
And high-boiling organic solvents as described in JP-A-59-178457 can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C.

The amount of high-boiling organic solvent used is 1 g of the dye-donor compound used.
On the other hand, it is 10 g or less, preferably 5 g or less. Also, 1 cc or less, further 0.5 cc or less, especially 0.
3cc or less is suitable.

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

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

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

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. For specific compounds preferably used, U.S. Pat.
No. 626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present 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. No. 4,500,626, columns 58 to 59 and JP-A-61-161.
No. 88256, pages (32) to (41), mordants described in
Nos. 244043 and 62-244036. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

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

The constituent layers of the light-sensitive material and the dye-fixing material include a plasticizer,
A high-boiling point organic solvent can be used as a slipping agent or a peeling property improving agent between the light-sensitive material and the dye-fixing material. Specific examples include those described in JP-A-62-253159, page (25), JP-A-62-245253, and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As an example, various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., especially carboxy modified silicone (trade name X-22-371
0) etc. are effective.

Also, silicone oils described in JP-A-62-215953 and Japanese Patent Application No. 62-23687 are effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

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

Examples of UV absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681), benzophenone compounds (JP-A-46-2784), and others. Sho 54-
There are compounds described in 48535, 62-136641, 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

As the metal complex, U.S. Pat. Nos. 4,241,155 and 4,2
45,018, No. 3 to 36, No. 4,245,195, No. 3, 8 to 8, JP-A Nos. 62-174741, 61-88256 (27) to (29), Japanese Patent Application No. 62-234103, 62. -31096, 62-230596 and the like.

Examples of useful anti-fading agents include JP-A-62-215272 (125)
(137).

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

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

A fluorescent whitening agent may be used in the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. An example is K. Veenkataraman's ed. “The Chemistry of Synt
hetic Dyes ", Vol. V, Chapter 8, and JP-A-61-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned.

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

Examples of the hardening agent used in the constituent layers of the light-sensitive material and the dye fixing material include U.S. Pat.No. 4,678,739, column 41, and JP-A-59-116655.
And hardening agents described in JP-A Nos. 62-245261 and 61-18942. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener Vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62) -234157 and the like).

In the constituent layers of the light-sensitive material and the dye-fixing material, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Specific examples of the surfactant are described in JP-A Nos. 62-173463 and 62-183457.

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 electrification, improving peelability and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
Nos. 62-135826 and the like, fluorine-based surfactants, or oil-based fluorine-based compounds such as fluorine oil or hydrophobic fluorine compounds such as fixed fluorine compound resins such as tetrafluoroethylene resin. To be

A matting agent can be used for the photosensitive material and the dye fixing material. Examples of the matting agent include compounds described on page 29 of JP-A-61-88256, such as silicon dioxide, polyolefin and polymethacrylate, and benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. Nos. 62-110065 and 62-110065.

In addition, in the constituent layers of the photosensitive material and the dye fixing material,
A hot solvent, an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like may be included. Specific examples of these additives are disclosed in JP-A-61-8
No. 8256, pages (26) to (32).

In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye-fixing material. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned promoting effects. For more information on these, see U.S. Pat.
No. 9 columns 38-40.

Examples of the base precursor include salts of an organic acid and a base that are decarboxylated by heat, a compound that releases amines by intramolecular nucleophilic substitution reaction, Rossen transfer or Beckmann transfer. Specific examples thereof are U.S. Pat. No. 4,511,493 and JP-A-62-
No. 65038.

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

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound); A compound that generates a base by electrolysis described in 61-232451 can also be used as a base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

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

The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

As the support of the light-sensitive material or dye fixing material of the present invention,
A material that can withstand the processing temperature is used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, 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 and the like are used.

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

In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can also be used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, a method of directly photographing landscapes and people using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., U.S. Pat.
The light source described in the column can be used.

Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between the polarization and the electric field, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), Lithium iodate, inorganic compounds typified by BaB ₂ O ₄ , urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivative, JP-A-61-53462, JP-A-62-53462
The compounds described in -210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

Further, the image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. It is possible to use image signals created using a computer represented by Signal, CG, CAD.

The light-sensitive material and / or the dye-fixing material may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye. As the transparent or opaque heating element in this case, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer step may be carried out simultaneously with the heat development,
It may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the transfer of the dye occurs only by heat, a solvent may be used to accelerate the transfer of the dye.

Further, as described in detail in JP-A-59-218443, JP-A-61-238056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also available. Useful. In this method, the heating temperature is preferably 50 ° C or higher and not higher than the boiling point of the solvent, for example, 50 ° C or higher when the solvent is water.
It is preferably 100 ° C or lower.

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

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

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

Further, in order to promote dye transfer, a method of incorporating a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature in the photosensitive material or the dye fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing material,
It may be built in both. Also, the built-in layer is an emulsion layer,
It may be any of an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer.

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

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

As a heating method in the developing and / or transferring step, it is brought into contact with a heated block or plate, or brought into contact with a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere.

The method described in JP-A-61-147244, page (27) can be applied to the pressure condition and the method of applying pressure when the light-sensitive material and the dye-fixing material are superposed and brought into close contact with each other.

Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247, JP-A-59-1
Nos. 77547, 59-181353, 60-18951, 62-259
An apparatus described in No. 44 or the like is preferably used.

Example 1 A method for preparing the emulsion (I) for the first layer will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin, 1 g of potassium bromide, and OH (CH ₂ ) ₂ S (CH ₂ ) ₂ OH in 800 ml of water)
Solution (I), solution (II) and solution (III) below were simultaneously added at an equal flow rate over 30 minutes. Thus, a monodispersed silver bromide emulsion to which a dye having an average grain size of 0.42 μm was adsorbed was prepared.

After washing with water and desalting, add 20 g of lime-processed ossein gelatin, adjust the pH to 6.4 and the pAg to 8.2, and keep the temperature at 60 ° C.
9 mg of sodium thiosulfate, 6 ml of 0.01% aqueous solution of chloroauric acid, 4
-Hydroxy-6-methyl 1,3,3a, 7-tetrazaindene
190 mg was added and chemical sensitization was performed for 45 minutes. Emulsion yield is 6
It was 35 g.

Next, the emulsion (II) for the third layer will be described.

Well-mixed aqueous solution (20 ml gelatin in 730 ml water)
g, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the following chemical A and kept at 60.0 ° C.), the following solutions (I) and (II) were simultaneously added at the same flow rate for 60 minutes. After the addition of the solution (I), a methanol solution (III) of the following sensitizing dye B was added. Thus, a monodispersed cubic emulsion having a dye having an average particle size of 0.45 μm adsorbed thereon was prepared.

After washing with water and desalting, 20 g of gelatin was added to adjust the pH to 6.4 and pAg.
After adjusting to 7.8, chemical sensitization was performed at 60.0 ° C. The chemicals used at this time were triethylthiourea 1.6 mg and 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene 100 mg.
The aging time was 55 minutes. The yield of this emulsion is
It was 635 g.

Next, how to prepare the emulsion (III) for the fifth layer will be described.

A well-stirred aqueous gelatin solution (20 g gelatin, 3 g potassium bromide, and HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH
₂ ) 0.3 g of ₂ OH was added and the mixture was kept at 60 ° C.), and the following solution (I) and solution (II) were added simultaneously over 30 minutes. After that, the following solution (III) and solution (IV) were simultaneously added over 20 minutes. After the addition is complete, potassium iodide 1% aqueous solution 30
cc was added, and then a solution of the following dye C (0.14 g) in methanol (70 cc) was added.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were prepared. , Chloroauric acid was added for optimum chemical sensitization. Thus, 600 g of a monodispersed octahedral silver iodobromide emulsion having an average grain size of 0.45 μm was obtained.

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

18 g of yellow dye-donor substance (1) ^* , electron donor (1)
Weigh 12g ^* , high boiling point organic solvent (1) ^* 9g, and add ethyl acetate 46
ml was added and dissolved by heating at about 60 ° C. to obtain a uniform solution.
This solution, 100 g of a 10% solution of lime-processed gelatin, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor substance dispersion.

Dispersions of magenta and cyan dye-donor materials were made using magenta dye-donor material (2) ^* or cyan dye-donor material (3) ^* as well as yellow dye-donor materials.

From these, a light-sensitive material 101 having the structure shown in Table 1 below was prepared.

The reducing agent (1) ^* was dispersed in the polymer (1) ^* and added by the following method.

Reducing agent (1) ^* 15 g and polymer (1) ^* 7.5 g 40 ml ethyl acetate
Was dissolved at about 60 ° C. into a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, and 12.6 ml of a 5% aqueous solution of a surfactant (3) ^* were mixed with stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes.

 Next, how to make the dye fixing material will be described.

A dye fixing material R-1 was prepared by coating on a polyethylene-laminated paper support in the constitution shown in the following table.

Next, the development inhibitor precursors shown in Table 2 were added to the second layer and the fourth layer of the light-sensitive material 101 in a molar ratio of 10% to the reducing agent (1) ^* to prepare light-sensitive materials 102 to 105. .
For comparison, the development inhibitor precursor AF-10 or AF-13 was added to each of the first layer, the third layer and the fifth layer at 0.02 mmol / min.
Light-sensitive materials 106 and 107 were prepared by adding m ² , 0.02 mmol / m ² and 0.03 mmol / m ² .

The development inhibitor precursors AF-13 and AF-19 were pulverized with a mill and added as a fine particle dispersion with an average particle size of 0.2 μm. Other development inhibitor precursors were the reducing agent (1) ^* or each dye-donating agent. It was dissolved with the substance and added as a co-emulsified dispersion.

For comparison, a second development inhibitor D having the following structure was used.
A light-sensitive material 108 was prepared by adding 1% of the reducing agent (1) ^* to the layer and the fourth layer in a molar ratio.

Development inhibitor D A tungsten light bulb is used for the color light-sensitive materials 101 to 108 having the above multi-layer structure, and the density is continuously changed B, G, R.
1 at 500 lux through gray and gray separation filters
Exposed for 2 seconds.

The exposed photosensitive material was immersed in water for 5 seconds, passed through a pair of rubber rollers to remove excess water, and then overlaid so that the dye fixing material R-1 was in contact with the film surface.

Using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was 75 ° C, the film was heated for 15 seconds. Next, peel it off from the dye fixing material, and apply blue, green, and B, G, R, and gray color separation filters on the fixing material.
Clear images of red and gray were obtained.

Table 2 shows the measurement results of the maximum density (D _max ) and the minimum density (D _mix ) of each color of cyan, magenta, and yellow in the gray part.

Is a development inhibitor precursor from Table 2 in the case of the present invention was added to the intermediate layer while D _max increases without increasing D _min is most light-sensitive material (No addition of development inhibitor precursor in the emulsion layer .106,107) and added photosensitive material a development inhibitor D in the intermediate layer (No.108) in conjunction with an increase in D _max
An increase in D _min was seen.

Example 2 The reducing agent (1) ^* in the intermediate layer was replaced with the reducing agent (2) ^* below.
(3) ^* is replaced with equimolar amount, and further, polymer (1) ^* is replaced with high boiling point organic solvent (1) ^* in equal weight, and photosensitive materials 201 to 208 (using reducing agent (2) ^* ) Or photosensitive material 30
1 to 308 (using reducing agent (3) ^* used).

Was treated in the same manner using the same dye-fixing material R-1 as in Example 1, the D _max increases without increasing D _min is mostly the case of the present invention with the addition of development inhibitor precursor in the intermediate layer On the other hand, both the light-sensitive material added to the emulsion layer and the light-sensitive material added with the development inhibitor in the intermediate layer showed an increase in D _min with an increase in D _max .

Example 3 Using the same emulsion, dye donating substance, electron donor, and electron transfer agent as in the light-sensitive material 101 of Example 1, a multi-layer color light-sensitive material 401 having the structure shown in Table 3 was prepared.

Unless otherwise specified, the same additives as in Example 1 were used.

 The organic silver salt emulsion was prepared as follows.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol. This solution was kept at 40 ° C. and stirred. To this solution, a solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added over 5 minutes. Then, excess salt was removed by a precipitation method. Thereafter, the pH was adjusted to 6.3 to obtain a 300 g yield of an organic silver salt dispersion.

Further, in the light-sensitive material 401, the development inhibitor precursors shown in Table 4 were added to the second layer and the fourth layer in a molar ratio of 10% to the reducing agent (1) ^* to prepare light-sensitive materials 402 and 403. For comparison, the development inhibitor precursor AF-23 was added to the first layer, the third layer and the fifth layer at 0.03 mmol / m ² respectively.
Then, a light-sensitive material 404 was prepared. The development inhibitor precursor was dissolved together with the reducing agent (1) ^* or each dye-providing substance and added as a co-emulsion dispersion.

Next, how to make the dye fixing material R-2 will be described.

Poly (methyl acrylate-co-N, N, N-trimethyl-
10 g of N-vinylbenzylammonium chloride) (the molar ratio of methyl acrylate to vinylbenzylammonium chloride was 1: 1) was dissolved in 200 ml of water, and uniformly mixed with 100 g of 10% lime-processed gelatin. A hardening agent was added to this mixed solution and uniformly coated on a paper support laminated with polyethylene in which titanium dioxide was dispersed to a wet film thickness of 90 μm. After drying this sample, it is used as a dye fixing material R-2 having a mordant layer.

The light-sensitive materials 401 to 404 were exposed to light through a wedge whose density was continuously changed in the direction perpendicular to the wavelength using a spectrograph, and then uniformly heated for 30 seconds on a heat block heated to 140 ° C.

After 20 ml of water per 1 m ² was supplied to the dye fixing material R-2 on the film surface side, the above-mentioned light-sensitive materials which had been subjected to the heat treatment were superposed on the fixing material so that the film surfaces were in contact with each other.

After passing through a laminator heated at 80 ° C at a linear velocity of 12 mm / sec, both materials were peeled off, and blue, green, and red spectrumgrams were obtained on the dye-fixing material according to the wavelength. Table 4 shows the results of measuring the densities of cyan and magenta in the blue light portion, cyan and yellow in the green light portion, and magenta and yellow in the red light portion.

From Table 4, it was found that color reproducibility was improved and a high density was obtained in the present invention in which the development inhibitor precursor was added to the intermediate layer. Incidentally, the light-sensitive material 404 having the development inhibitor precursor added to the emulsion layer produced color turbidity.

Claims (2)

(57) [Claims] 1. A heat-developable color having on a support at least a light-sensitive silver halide, a binder, a diffusible reducing agent, and a non-diffusible, reducible dye-donor compound which releases a diffusible dye when reduced. The photosensitive material has at least two photosensitive layers having different color sensitivities, and
A heat-developable color having layers each containing at least one diffusion-resistant development inhibitor precursor capable of releasing a diffusion-resistant reducing agent and a diffusion-resistant development inhibitor between two photosensitive layers. Photosensitive material. 2. A color image forming method, which comprises heat-developing the heat-developable color light-sensitive material according to claim 1 after image exposure or simultaneously with image exposure.