JPH02110557A - Heat developable color photosensitive material and image forming method using this material - Google Patents

Abstract

PURPOSE:To increase image densities and to improve color reproducibility by providing layers contg. respectively at least one kind of diffusivity resistant reducing agents and diffusivity resistant development restrainer precursors which can release diffusive development restrainers between two photosensitive layers which are different in color sensitivity from each other. CONSTITUTION:At least two photosensitive layers which are different in color sensitivity from each other are provided to the heat developable color photosensitive material having a photosensitive silver halide, binder, diffusive reducing agent, and a reducible dye donative compd. which releases the reduced diffusive dye on a base. The layer contg. respectively at least one kind of the diffusivity resistant reducing agents and the diffusivity resistant development restrainer precursors which can release the diffusive development restrainers is provided between these two photosensitive layers. This photosensitive material is subjected to heat development after or simultaneously with image exposing. The image density and color reproducibility are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-developable color photosensitive material and an image forming method using the same.

(Background technology and its problems) Heat-developable photosensitive materials and materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, for example, ``Fundamentals of Photographic Engineering'' Non-Silver Salt Photography! ! (Published by Corona Publishing, 1982), pages 242 to 255, and US Pat. No. 4,500,626.

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

For example, US Pat. No. 4,559,290 describes the so-called DR
A reducing agent or its precursor is made to coexist with an oxidized R compound that does not have the ability to release a dye, and the reducing agent is oxidized according to the exposure amount of silver halide by 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 2207
No. 46, Technical Report 876199 (Vol. 12, No. 22) describes compounds that release diffusible dyes by a similar mechanism.
A heat-developable color photosensitive material using a non-diffusible compound which releases a diffusible dye upon reductive cleavage of an N--X bond (X represents an oxygen atom, nitrogen atom or sulfur atom) has been described.

However, it has been found that when the above-mentioned reducible dye-providing compound is used in combination with a silver halide emulsion together with a reducing agent or its precursor, there is a problem of high staining of color images.

In order to suppress staining in a 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,
It is effective to use an electron transfer agent that is a diffusible reducing agent, but the generated electron transfer agent radicals diffuse into other layers with different color sensitivities and cross-oxidize the electron donors there, resulting in poor image quality. This causes a decrease in density and worsens color reproduction.

For this reason, attempts have been made to provide an intermediate layer between photosensitive layers having different color sensitivities or to include a reducing substance in this intermediate layer (Japanese Patent Application No. 62-279842, etc.).
In the heat-developable diffusion transfer type photosensitive material 4 of the present invention, there are restrictions on the amount of binder in the intermediate layer and the amount of reducing substance added in terms of image forming speed, resolution, film quality, etc., and further improvements are desired. be done.

In addition, photosensitive materials containing the above-mentioned diffusible reducing agent tend to cause fog on silver halide during thermal development, and as a result,
This results in a decrease in malting and an increase in the minimum concentration (Dmin).

As a countermeasure against this, a development inhibitor (
It has been proposed to add an anti-fogging agent) or to use a development inhibitor precursor.
No. 84, No. 62.310028, etc.).

However, in this case, the density decreases and the photographic properties of the light-sensitive material tend to change during raw storage, and further improvements are desired.

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

(Structure of the Invention) The object of the present invention is to provide at least a photosensitive silver halide, a binder, a diffusible reducing agent, and a diffusible reducing agent on a support.
A heat-developable color photosensitive material having a reducible dye-providing compound that releases a t-character dye, which has at least two photosensitive layers having different color sensitivities, and has a diffusion-resistant property between the two photosensitive layers. A heat-developable color photosensitive material characterized by having a layer containing at least one type of reducing agent and a diffusion-resistant development inhibitor precursor capable of releasing a diffusible development inhibitor; This was achieved by a color image forming method characterized by carrying out heat development at the same time as image exposure.

As the development inhibitor BRE JJ-SER of the present invention, there may first be mentioned a compound represented by the following formula [l] which releases a development inhibitor upon reduction.

General formula (N PWR → Time) TA F In the formula, PWR represents a group that releases (Time)-r-8F upon reduction, and Time follows by triggering the reduction of P141'i. Represents a group that releases ^1+ through reaction.

L represents an integer of O or 1.

AF represents a group that acts to inhibit development after being released.

PWI first? I will explain in detail.

PWR is based on U.S. Pat. No. 4,139.31119, or U.S. Pat.
No., JP-A-59-185333, JP-A No. 57-84453
Even if it corresponds to a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. Good, U.S. Patent 4,232,10
No. 7, JP-A No. 59-101649, Research Disclosure (1984) IV, No. 24025, or JP-A No. 61-88257, after being reduced, the photographic reagent is released into the molecule by an electron transfer reaction. It may correspond to a part containing an electron-accepting quinonoid center in a compound to which the electron-accepting quinonoid center and a carbon atom linking it to a photographic reagent.
No. 2530, U.S. Pat. No. 4,343.1393, U.S. Pat.
No. 619,884, the single bond is cleaved after reduction to release the photographic reagent, and the aryl group substituted with an electron-withdrawing group and the atom (sulfur atom or carbon or a nitrogen atom). Also, US Patent 4,
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. 450,223. , U.S. Patent 4,609,61
It may correspond to the geminal dinitro moiety in the dinitro compound that beta-desorbs the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in No. 0.

In addition, a compound having SO□-X (X represents oxygen, sulfur, or nitrogen) and an electron-withdrawing group in one molecule as described in Japanese Patent Application No. 62-106885, Japanese Patent Application No. 62106
No. 895, a compound having a po-π bond (X has the same meaning as above) and an electron-withdrawing group in one molecule, patent application No. 1989-
C-χ゛ bond X' in one molecule described in No. 106887
is synonymous with X or represents -3O□-) and a compound having an electron-withdrawing group.

Also, Japanese Patent Application No. 62-319989, No. 62-3207
A group described in No. 71 that releases a diffusible dye by cleavage of 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, the general formula (1
) Among the compounds represented by the general formula (+-1), those represented by the general formula (+-1) are preferred.

General formula (1-1) (Timeh-AP is bonded to at least one of 17101.RI°= or EAG.

The part corresponding to the PWR of the 11R formula (11) will be explained.

X represents a group (-N(1?'')-) containing an oxygen atom (-0-), a sulfur atom (-S-), or a nitrogen atom.

Rlol, HI@t and R10' represent a group other than a hydrogen atom or a simple bond.

R1111, R10! Groups other than hydrogen atoms represented by You may do so.

R101 and R103 are preferably interchangeable or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, and the like. RI6
1 and Rlol preferably have 1 to 4 carbon atoms.

1711111 is preferably a substituted or unsubstituted acyl group or sulfonyl group. For example, R11B+,,111
It is the same as the acyl group and sulfonyl group mentioned in 03. The number of carbon atoms is preferably 1 to 40.

11161, R162) and R16' may be bonded to each other to form a five- or six-membered ring.

As X, oxygen is particularly preferred.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula (1-1
) Among the compounds represented by the general formula (+-23), those represented by the general formula (+-23) are preferred.

- Clothes cost (1-2) (Time) -r-AP binds to at least one of R104 and [EAG.

X has the same meaning as above.

R1114 represents an atomic group that is bonded to X or a nitrogen atom to form a five- or six-membered monocyclic or condensed heterocycle including the nitrogen atom.

are listed and shown together with the location of EAG.

The precursor of the present invention is preferably immobile per se in the photographic layer, so that [80, R1111,
Ply! , R+64 or CX (7) position (patent EAG
It is desirable to have a ballast group having 8 or more carbon atoms at position ).

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. As EAG, the following general formula (A,)
A group represented by is preferred.

- Layering (A) In the general formula [A], (1) or Z2) represents an atomic group forming a three- to six-membered aromatic group together with z, and n represents an integer of 3 to 8.

C3;-z:1-1V-;-Zl-Z4-, Vs;
-Zl-Z4-Zs-2V; -Zl-Z4-Z
s-Zb-, L+; -L-Za-Zs-L-L-1
Vs;-Z)-Z4-Z, -Z6-Z, -Za-.

4.

Alternatively, it represents -3O2-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Each Sub may be the same or different, or They may be combined with each other to form a three- to six-membered saturated or unsaturated carbocyclic or heterocyclic ring.In the general formula (A), the sum of the Hament direct substituent constant sigma rose of the substituents is +0.50 or more,
More preferably +0.70 or more, most preferably +0
．． Select Sub so that it is 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 atomyl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire 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.

Specific examples of EAGs are further described in European Patent Publication No. 220746A2 6-7.

Time represents a group that releases 8F through a subsequent reaction, potentially causing cleavage of a nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bond.

Various groups represented by Ti+we are known, for example, JP-A-61-147244, pages (5) to (6), and JP-A-61-147244, pages (6) and 61-
No. 236,549, pages (8) to (14), and European Patent No. 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 that releases a development inhibitor by the action of a base may be used. Among them, the following three types are preferable.

(Type I) >C=C< group, >C.0 group, >C=S group, >C=N,,
group and >C=N''; group, and the development inhibitor (hereinafter referred to as AF) is formed by the attack of a base or a base released from a base precursor onto the carbon atom of these functional groups and the subsequent reaction. ) release precursor compound.

Eight F following base attack on the carbon atoms of these functional groups
The forms of emission are: release due to cleavage of bonds directly bonded to these carbons: release due to cleavage of other bonds with electron transfer; intramolecular nucleophilic release with or without electron transfer. Release by cleavage of other bonds by attack; release consisting of a plurality of the above-mentioned reaction types; furthermore, release via timing groups, etc.

(Type 2) Deprotonation by a base released from a base or a base precursor, followed by a precursor compound that releases AP by reaction.The reaction format of AP release in such a precursor compound is as described above (Type 1). Same as mentioned above.

(Type 3) Precursor compound having 8F and releasing 8F by attack of a base on the sulfur or phosphorus atom of these functional groups and subsequent reaction.

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

Particularly preferred as the development inhibitor precursor are compounds in which the hydrogen atom of the mercapto group of a development inhibitor having a mercapto group is substituted with a group having a functional group of the above (Type 1) to (Type 3).

Specifically, examples of precursor compounds belonging to (Type 1) include JP-B No. 4B-9968, JP-A No. 52-8
No. 828, No. 57-82834, U.S. Patent No. 3.31
1,474, 3,615,617, etc., and development inhibitor precursors: Japanese Patent Publication No. 54-39727, U.S. Patent No. 3,674
, No. 478, No. 3,932,480, No. 3,99
3.661, JP-A-58-1140, JP-A No. 58-20
Precursor that releases 8F by cleavage of acetyl group and subsequent electron transfer or further decarboxylation as described in No. 9736, No. 59-225168, etc.: Tokko Sho 5
7-22099, U.S. Patent No. 4,199゜354, JP-A-55-53330, etc. Precursors that release AF by ring cleavage and subsequent intramolecular ring-closing reaction: JP-A-55-53330 Precursors that release molecules by hydrolysis and subsequent intramolecular ring closure reaction described in the specification: JP-A-57-76541, JP-A-59-13
No. 5949, No. 57-179842, No. 59-343
No. 4, No. 59-137945, No. 59-140445
Precursor that releases AP through ring cleavage, subsequent electron transfer, and decarboxylation as described in No. 1, etc.: Research Disclosure Magazine 15, 162 (1976), JP-A-56-77842, U.S. Patent No. 4.307 ,175
Precursors that release 8F by nucleophilic attack of a base on a carbon-carbon double bond and subsequent elimination as described in Book No. 5I and the like can be mentioned.

Specific examples of precursor compounds belonging to (Type 2) include, for example, Japanese Patent Publication No. 55-34927, U.S. Patent No. 4009
．． No. 029, Special Publication No. 55-9696, No. 55-173
No. 69, JP-A-59-105640, JP-A No. 59-105
641, No. 59-105642, etc. Precursors that release molecules using the so-called reverse Michael reaction: Japanese Patent Publication No. 54-39727, Japanese Patent Publication No. 57-13594
No. 4, No. 57-135945, No. 57-136640
No., No. 58-976, No. 58-1139, etc. >N-H or -OH dissociates to generate an anion, and AP is released as a quinone methide-like compound is generated due to intramolecular electron transfer. Precursor II JP-A-59-202
Examples include a method using ring opening of benzisoxazole to O-cyanophenol described in No. 459.

Examples of precursor compounds belonging to (Type 3) include the sulfonyl group-containing precursor compounds described in JP-A-52-8828.

In the present invention, development inhibitor precursors represented by the following general 2 ([1) or (Tel) are particularly preferred.

-Layer formation (Ill OHOH R'-3-C11, -C1l□-5Q, -(CH,)T
-CIl→L-C1th-(CII2)--5Ow-C
L-C1h-5-R' In the above layer formation [■], R5
and R6 may be the same or different and each represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, or nitrogen-containing heterocyclic group, preferably a substituted or unsubstituted represents an aryl group or a nitrogen-containing heterocyclic group.

Examples of substituents in this case include alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkoxy groups,
Aryloxy group, alkylthio group, arylthio group,
Acyl group, alkoxycarbonyl group, amino group, N-substituted amino group, acylamino group, carbamoyl group, N-substituted rubamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, Examples include N-Itk sulfamoyl group, cyano group, nitro group, and halogen atom.

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

L represents a single bond or a substituted or unsubstituted divalent group, p and q are each 1 or 2, and n is O or 1.

-a The divalent group represented by L in formula CII) is preferably an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -0-1-N-1-5--5O- 1SO,
A divalent group represented by --C- or a combination of two or more of these divalent groups is preferred.

Here, R7 is a hydrogen atom, a carbon fil-10 alkyl group (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, etc.), a C6-10 aryl group (e.g., phenyl group, etc.), or Represents an aralkyl group having 7 to IO carbon atoms (eg, Hensyl group, etc.).

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.

- Stratification (I[l) I1 1゜In the above - Stratification [111], R5 and R''' have the same meaning as the general formula [g]. R1' and R9 may be the same or different from each other. , each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a and b are each an integer from O to 3, and may be the same or different. L may be different and each represents an ester bond, a substituted or unsubstituted amide bond, or an ether bond;
゛ represents an alkylene group, a phenylene group or a xylylene group. Furthermore, when x1 or x2 is an amide group,
The substituents on nitrogen are bonded to each other to form L′ and X′,
``may constitute a heterocycle together with a portion of each of them.

n and m are each an integer of 0 or l.

Examples of the alkyl group of R11 and R include a methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 5ec-butyl group, and L-butyl group.
@, R9 is preferably a hydrogen atom or a methyl group.

XI and X! When is an amide group, examples of the substituent include an alkyl group and an aryl group, and the heterocycle composed of L' and a part of each of X11x2 may be substituted. Examples include a hydrotriazine ring, an imidacilline ring, a piperazine ring or a perhydropyrimidine ring, and in particular the perhydrotriazine ring may be substituted. Examples of the substituent in this case include R'-5-CHzCH*-5ot-GCHfCHf- group (wherein R5, R8, and a have the same meanings as above).

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

x1 and x2 are preferably amide bonds or ether bonds.

Other development inhibitor precursors of the present invention include the following -
Examples include compounds (DIR compounds) that release a development inhibitor upon oxidation and are represented by stratification (IV).

General formula (IV) A-(Time)-T-A F In the formula, A is oxidized to form +Time)r-AP
It is a redox mother nucleus that makes it possible to release .

Ti1ae, t % The definition of AP is the general formula [1]
It is similar to

A in general formula (IV) will be explained in more detail.

Examples of the redox nucleus represented by A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, l,2-naphthalenediol, l,4-
naphthalene diol, ■, 6-naphthalene diol, 1
．． Examples include 2-aminonaphthol, 1.4-aminonaphthol, and 1.6-aminonaphthol. At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 carbon atoms. Examples of the sulfonyl group include substituted or unsubstituted aliphatic sulfonyl groups and aromatic sulfonyl groups.

Examples of the acyl group include substituted or unsubstituted aliphatic acyl groups and aromatic acyl groups. The hydroxyl group or amine group forming the redox mother nucleus may be protected with a protecting group that can be removed during development. Examples of the protecting group include those having 1 to 25 carbon atoms, such as acyl. group, alkoxycarbonyl group, carbamoyl group, and JP-A-59-197037, JP-A-59-201057
The number is 31! The basics are given. Furthermore, if possible, this protecting group may be bonded to the substituent A described below to form a 5.6- or 7-membered ring.

The redox nucleus represented by A may be substituted with an appropriate compatible group at an appropriate position. Examples of these substituents include those having 25 or less carbon atoms, such as alkyl groups, aryl groups, alkylthio groups, arylthio groups, alkoxy groups, aryloxy groups, amino groups, hydroxy groups, acyloxy groups, amide groups, and sulfonamide groups. 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 CTim
e) Ding AP etc. These substituents may be further substituted with the substituents described above. These substituents may also be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle, if possible.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, O-aminophenol, 1.
4-naphthalenediol, 1. Examples include 4-aminonaphthol. More preferred examples of A include hydroquinone, catechol, p-aminophenol, and 0-aminophenol. Most preferred as A is hydroquinone.

Preferred specific examples of A in general formula (IV) are shown below, and in each structural formula (time) indicates the position to which r-AP is bonded.

0H Shi■3 Shi113 υH H O1+ (River t-CJI□ As a diffusible development inhibitor represented by AF, the carbon number is 1.
5 or less, preferably 10 or less, compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically 1-phenyl-5-mercaptotetrazole, 1-(4- carboquinphenyl)-5 mercaptotetrazole, 1-(3
-hydroxyphenyl)-5-mercaptotetrazole, 1(4-sulfophenyl)-5-mercaptotetrazole, 1-(3-sulfophenyl)-5-mercaptotetrazole, 1-(4-sulfamoylphenyl)-5
-Mercaptotetrazole, (3-hexanoylaminophenyl)-5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1-(2-carboxyethyl)5-mercaptotetrazole, 2-methyl 5-mercapto- 1,3,4-thiadiazole, 2-
(2-carboxyethylthio)-5-mercapto-1,
3,4-thiadiazole, 3-methyl4-phenyl-5
-Mercapto-12,4 triadur, 2-(2-dimethylamineethylthio)-5-mercapto-1,3,4
-thiadiazole, 1-(4-n-hexylcarbamoylphenyl)-2-mercaptoimidazole, 3-acetylamino-4-methyl-5-mercapto-12,4-
Triazole, 2-mercabutohensoxazole, 2
-Mercaptohenzimidadur, 2-mercaptobenzothiazole, 2-mercap)-6-nitro-13-henzoxadur, ■-(l-naphthyl)-5-mercaptotetrazole, 2-phenyl-5-mercapto-1
34-Oxadiazole, i (3-(3-methylureido)phenyl)-5-mercaptotetrazole, 1-
(4-nitrophenyl)-5-mercaptotetrazole, 5-(2-ethylhequinanoylamino)-2-mercaptohenzimidazole, etc.), substituted or unsubstituted! 1a
mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3,3a, 7-chitrazaindene, 6-methyl-2-hensyl-4-mercapto-13
, 3a, 7-chitrazaindene, 6-phenyl 4-mercapto-1,3,3a, 7-chitrazaindene, 4.6
-dimethyl-2-mercapto 1.3.3a, 7-chitrazaindene, etc.), substituted or HA-free mercaptopyrimidine iJt (specifically 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, mercapto-4-propylpyrimidine, etc.). Heterocyclic compounds capable of producing iminosilver, such as substituted or unsubstituted penditriazoles (specifically, henchitriazole, 5-nitrohencitriazole, 5-methylbenzotriazole, 5,6-cyclohenzotriazole, 5- Bromobenzotriazole, 5-methoxyhencytriazole, 5-acetylaminohencytriazole, 5-n-butylhencytriazole, 5-nitro-6-chlorohencytriazole,
56-dimethylbenzotriazole, 4,5.6 futetrachlorhenzotriazole, etc.), substituted or unsubstituted indazole R (specifically intasol, 5-
Nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, 3-cyanoindazole, 3-n-phthylcarhamoylindazole, 5-2[・ro-3methanesulfonylindazole, etc.), substituted Or unsubstituted henraimidazole (specifically,
5-nitrohenzimidazole, 4-nitrohentimidazole, 56-cyclohenzimitazole, 5-
cyano-6-chlorpenzimitazole, 5-trifluoromethyl-6-chlorpenzimidazole, etc.).

Specifically, 1-(3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1(4-phenoxycarbonylphenyl)5-mercaptotetrazole, 1-
(3-maleinimidophenyl)5-mercaptotetrazole, 5(phenoxorubonyl)hencytriazole, 5-(p-cyanophenoquinecarbonyl)hencytriazole, 2-phenoxorponylmethylthio-5
-mercapto-1534-thiadiazole, 5-nitro-3-phenoxycarbonylindazole, 5-phenoxycarbonyl-2-mercaptobenzimidazole,
5-(2,3-dichloropropyloxycarbonyl)benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5-(butylcarbamoylmethoxycarbonyl)benzotriazole, 5-(butoxycarbonylmethoxycarbonyl)benzotriazole, 1-(
4-benzoyloxyphenyl) 5-mercaptotetrazole, 5-(2-methanesulfonylethoquinecarbonyl)-2-mercaptobenzothiazole, 1- (4-
(2-chloroethoxycarbonyl)phenyl)-2-mercaptoimidazole, 2-(1-[thiophene-2
=ylcarbonyl)propyl]thio-5-mercapto-
1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1-(3-vinylcarbonylphenyl)-5-mercaptotetrazole, 5-succinimidomethylhensitriazole, 2-(4-succinimidophenyl)5-mercapto- 1,3,4-oxadiazole, 314-(=,nzo1,2-isothiazole3-oxo-1,1-dioxy-2-yl)phenyl)-5-mercapto-4-methyl-1,2 Examples include 4-triazole, 6-phenoxycarbonyl 2-merkabutohentoxazole, and the like.

These development inhibitors have a site (-5H) that causes development inhibition.
(S atom of the imino group, N atom of the imino group, etc.) to the precursor body. Particularly preferred development inhibitor precursors are compounds capable of releasing a development inhibitor having a mercapto group.

In addition, the development inhibitor precursor of the present invention has carbon atoms of 16 or more, preferably 20 or more, or has a solubility in water at 25°C of 0.1 or less, preferably 0.01 or less, in order to have diffusion resistance. Preferably.

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 Japanese Patent Publication Nos. 47-44805 and 54-17369. No. 55
-9696, 55-34927, 54-397
No. 27, JP-A-57-135944, JP-A No. 574359
No. 45, No. 57-136640, No. 55-53330
No. 57-76541, No. 57-135949,
No. 57-179842, No. 62-215270, No. 61-67851, No. 61-124941, No. 61
-147249, 61-185743, 61-
No. 184539, No. 61-147244, No. 61-1
No. 88540, No. 61-182039, No. 61-18
No. 5744, No. 61-236548, No. 61-267
No. 045, No. 61-267041, No. 61-2691
No. 47, No. 61-269143, No. 61-26914
No. 8, No. 61-269147, patent application No. 62-3100
It can be synthesized into a container according to the method described in No. 28.

The amount of the development inhibitor precursor used in the present invention varies depending on the compound and the system used, but in each intermediate layer, the amount used is 0.001 mmol to 5 mmol, preferably 0.01 mmol to 0.5 mmol, per 1M of support. 5 mmol, and in each intermediate layer from 0.005 mol to 10 mol, preferably from 0.01 mol to 1 mol, per mol of diffusion-resistant reducing agent in that layer.

In the present invention, the development inhibitor precursor can be added to the emulsion layer, colorant layer, protective layer, etc., if necessary.

Compounds described in the following patents can be used as reduction rules for diffusion resistance used in the intermediate layer of the present invention.

U.S. Patent Nos. 2,360,290 and 2,403,721
No. 2゜418.618, No. 2,701.197, No. 2,728.659, No. 2,735,765,
No. 2,732.300, No. 3,700,453, Special Publication No. 59-37497, No. 56-21145, No. 5
No. 1-12250, JP-A No. 59-202465, No. 5
No. 5-72158, No. 5543521, No. 57-22
No. 237, No. 5B-156932, No. 595247, No. 62-103638, West German Patent Publication (OLS) 2
．． No. 732,971, Japanese Patent Application No. 62-279842, Japanese Patent Application No. 63-197566, etc.

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

General formula (V) General formula (Vl) In the formula, )ill is a hydroxyl group, -NR"R" -NIIS
OJ" wo.

R11, 1712) Ill, R14 is a hydrogen atom: a halogen atom (e.g. chlorine atom, bromine atom, etc.) aliphatic group (
For example, an alkyl group having 1 to 22 carbon atoms (such as a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, lopentyl group, n-decyl group, terL-decyl group, n-dodecyl group, 5ee
-dodecyl group, tert-dodecyl group, n-pentadecyl group, 5ec-pentadecyl group, ts+rt-pentadecyl group, 5ec-octadecyl group, tert-octadecyl group), a straight chain or branched alkyl group having 1 to 22 carbon atoms. Substituted alkyl group [substituents include halogen atom, hydroxy group, alkokene group, substituted amino group (including alkyl or arylsulfamoyl group and alkyl or arylcarbamoyl group), cyano group, 2-
Hydroxyethyl group, 3-methoxypropyl group, 3-n
-butylsulfamoylpropyl group, etc.)], an alkenyl group having 3 to 22 carbon atoms (e.g., allyl group, etc.)
, cycloalkyl group having 5 to 12 carbon atoms (e.g. cyclohexyl group, etc.), aralkyl group having 7 to 22 carbon atoms (e.g. hensyl group, phenethyl group, 4-methylphenylethyl group, etc.), aryl group (e.g. phenyl moiety or hydroxyl group) a phenyl group substituted with a group, an alkyl group, an alkoxy group, an arylsulfonyl group, etc.) an alkoxy group, such as an optionally substituted alkoxy group having 1 to 22 carbon atoms (such as a methquin group, an ethoxy group, an n-
butoquino group, n-dodecylthio group, etc.) Aryloxo group, for example, an optionally substituted aryloxo group having 6 to 22 carbon atoms (for example, phenoxy group, 4-
n-butoxyphenyloxy group); alkylthio group, for example, an optionally substituted alkylthio group having 1 to 22 carbon atoms (for example, methylthio group, ethylthio group, n-pentylthio group, n-dodecylthio group, n-pentadecylthio group) , 5-chloropentylthio group, etc.); Arylthio group, e.g., an optionally substituted arylthio group having 6 to 22 carbon atoms (e.g., phenylthio group, 4-nitrophenylthio group, etc.); Sulfonyl group, e.g., carbon number 1 -30 alkyl or arylsulfonyl group (e.g. n-)decylsulfonyl group); Acyl group, e.g. acyl group having 2 to 30 carbon atoms (e.g. stearoyl group); Carbamoyl group, e.g. carbamoyl having 2 to 30 carbon atoms groups (e.g. 2,5-di-L-amylphenoxyethylcarbamoyl group); ester groups, e.g. 2 to 30 ester groups (e.g. p-
(t-octyl)benzyloxycarbonyl group); Sulfamoyl group, such as a sulfamoyl group having 1 to 30 carbon atoms (such as octadecylsulfamoyl group); Amide group, such as an optionally interchangeable amide group having 2 to 22 carbon atoms (e.g. acetamido group, benzoylamino group,
α-(2,4-di-L-amylphenoxy)bucunamide group, etc.); Ureido group, for example, an optionally substituted ureido group having 1 to 22 carbon atoms (for example, N,N-diethylureido group, etc.); Urethane group , for example, an optionally substituted urethane group having 2 to 22 carbon atoms (eg, phenoxycarbonylamino group, butoxycarbonylamino group, etc.); sulfo group; carboxyl group, etc.

RIS and ItIth represent a hydrogen atom, an aliphatic group, and an aryl group (the aliphatic group and the aryl group have the same definitions as in R1 to R14).

l1llff is an aliphatic group (for example, an alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, n-decyl group, n-
straight chain and branched alkyl groups such as dodecyl group and i-pentyl group), substituted alkyl groups having 1 to 22 carbon atoms [those having a halogen atom (chlorine atom or bromine atom) as a substituent,
For example, 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.; having a sulfonyl group such as ethanesulfonylmethyl74,
n-7'tylsulfonylethyl group, arylsulfonylbutyl group, etc.; those having an alkoxy group (e.g. methoxy group, ethoxy group, n-butoxy group, n-hexyloxy group, etc.), such as methoxymethyl group, methoxyethyl group, Ethoxyethyl group, n-butoxyethyl group 1.3
-Methoxypropyl group, n-hexyloxyethyl group, etc.: Those with an alkylthio group (e.g. ethylthio group, ethylthio group, n-hexylthio group, etc.), such as methylthiomethyl group, methylthioethyl group, 3-ethylthiopropyl group , n-hexylthioethyl group, etc.; or those having substituted amino groups, such as 4-(N,N-dimethylamino)butyl group, 5-acetamidopentyl group, 4-methylsulfonylaminobutyl group, anilinomethyl group, etc.] , cycloalkyl group (e.g. cyclohexyl),
For example, an aralkyl group which may have a substituent having 7 to 22 carbon atoms (e.g., hensyl group, 4-methylbenzyl L4-chlorobenzyl group, phenethyl group, 4-methylphenylethyl group, etc.), a substituted amino group (e.g. An amino group mono- or di-substituted with an alkyl group or an aryl group having 1 to 20 carbon atoms (e.g. dipropylamino group), or an aryl group such as a phenyl group or a substituted phenyl group (as a substituent, a halogen atom (e.g. those with chlorine atoms, bromine atoms),
For example, 4-chlorophenyl JL4.4-bromophenyl!
, 2-chlorophenyl group, etc.; those having a hydroxy group, such as 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2,5-dihydroxyphenyl group, etc.; those having an optionally substituted alkyl group, such as 4- Methylphenyl group, 4-1-propylphenyl 1.4-n-dodecylphenyl L2-chloro-4-methylphenyl group,
4-chloromethylphenyl group, 2,5-dihydroxydi-4-alkylphenyl group, etc.; those having an optionally substituted alkoxy group, such as 4-methoxyphenyl group, 4
-Ethoxyphenyl group, 4-n-propoxyphenyl group, 2-methyl-4-methoxyphenyl group, 3-methoxyphenyl'J, 4n-pentyloxyphenyl group, 4-
n-dodecyloxyphenyl group, 3-n-pentadecyloxyphenyl group, etc.; those having an optionally substituted alkylthio group, such as 4-methylthiophenyl group, 4-
Ethylthiophenyl 5.4-n-methylthiophenyl group, 3n-hexylthiophenyl group, 3-n-denruthiophenyl group, etc.: those having an alkoxycarbonyl group,
For example, 4-methoxycarbonylphenyl group, 4-ethoxycarbonyl-2-chlorophenyl group; Those with carboxy group, such as 4-carboxyphenyl group; Those with carbamoyl group, such as 4-carbamoylphenyl group, 4-methylamino carbonylphenyl group, 2-
Chloro-4-(N,N-diethylaminocarbonyl)phenyl group, etc.; Substituted amino group (substituents include alkyl group, acyl group derived from aralkylinic acid or sulfonic acid, etc.)
Each of these substituents may be further substituted),
For example, 4-methylaminophenyl group, 4- (N,N-
diethylamino)phenyl group, 4(N-ethyl-N-hensylamino)phenyl group, 4-acetamidophenyl group, 4-methanesulfonylaminophenyl%, 3-n-
Heptanoylaminophenyl group, 3-phenylsulfonylamylaf-1-nyl group, etc.; Those with nitro group, such as 4-nitrophenyl group, 4-nitro-2-methylphenyl group, 2-chloro-4-nitrophenyl group, etc. ;Those having a cyano group, such as a 4-cyanophenyl group;Those having an acyl group, such as a 4-acetylphenyl group, a 2-
Methyl-4-acetylphenyl group, 4-hendiylphenyl group, etc.; those having a sulfonyl group, such as 4-methanesulfonylphenyl group, 2-chloro-4-ethanesulfonylphenyl group, 4-phenylsulfonylphenyl group, 3- Those having a sulfamoyl group such as (2,5-dihydroxy-4-tertpentylphenyl)sulfonylphenyl group, such as 3-sulfamoylphenyl group,
3-(n-butylaminosulfonyl)phenyl group, 2-
Chloro-4-phenylaminosulfonylphenyl group, etc.; those with a sulfo group, such as 4-sulfophenyl group,
2-chloro-5-sulfophenyl group, etc.).

HI3 represents an aryl group (the details of the aryl group are the same as R1+).

x1! , I13 and X14 represent a group selected from the same groups as x1 or a group selected from the same groups as R1, and at least one of Xlz and XI4 represents a group selected from the same groups as x1. When both I12 and X'' are groups selected from the same groups as X11,
x'' represents a group selected from the same bracket as llill.

1711 and R+2, R+2 and X14 may jointly form a fused ring, and RIS and Rlth may jointly form a heterocycle.

In order to make the compound itself diffusion resistant, the compounds represented by general formulas (V) to (Vl) have R11 in the compound,...
The total number of carbon atoms in Rill and x1 to xlj is preferably at least 8 or more, more preferably 10
15 or more, more preferably 15 or more. As another means of making the compound resistant to expansion 1141, - stratification (V)
The compound of ~(V[) may form a bis body or a tris body linked by any of R1-R111, or R1
- It may be an oligomer or polymer linked to a polymer by any one of -R111.

Among general formulas (V) to (Vl), those of -layer structure (V) are particularly preferred.

In the 1C formula (V), X11 is preferably a hydroxyl group or a NHSO□R1'' group, with a hydroxyl group being particularly preferred.

In the general formula (V), it is preferable that xlff is a group selected from the same groups as R1, and furthermore, XI2)x''' is li
A group selected from the same groups as l+, where X14 is X1
Particularly preferred is a group selected from the same groups as 1.

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

0H x:y=55:45 C+aH+t(t) As for the synthesis method of the diffusion-resistant reducing agent used in the present invention, the method described in the above-mentioned patent can be used.

The amount of the reducing agent of the present invention added is 0.01 mmol to 10 mmol per layer of the support in each intermediate layer, preferably 0.1 mmol to 5 mmol, and 0.8 mmol to 10 mmol per 1 g of binder in each intermediate layer. mmol~10
The reducing substance of the present invention in an amount of 6 mmol, preferably 0.1 mmol to 5 mmol, can also be added to the protective layer if necessary. When added to the protective layer, the amount added is
0.0% per gram of binder in the i-layer. Ol mmol to 10 mmol, preferably 0.1 mmol to 5 mmol.

In the case where there are multiple intermediate layers in the present invention, the development inhibitor precursor and/or diffusion-resistant reducing agent added to each intermediate layer may be the same or different, and multiple compounds may be used in combination. good.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a reducible dye-providing compound, and a binder on a support, and further contains an organic metal salt oxidizing agent, etc. as necessary. You can cross it. These components are often added to the same T3, but if they are in a state where they can react, they can be divided into separate layers and added. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and yellow, a combination of at least three silver halide emulsion layers each sensitive to a different spectral region is used. .

For example, there are combinations of three layers of bluestone, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in a variety of arrangements known from conventional color 13 photoreceptors.

Furthermore, each of these photosensitive layers may be divided into two or more layers, if necessary.

The heat-developable photosensitive material 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 bank stone.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
The silver halide emulsion used in the present invention may be any of 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. It may be an emulsion,
The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofog. Further, the silver halide emulsion may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. Particle size is 0
．． 1 to 2-1 is particularly preferably 0.2 to 1.5. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other. Specifically, U.S. Patent No. i, 500.626 No. 5041111
, No. 4.628.021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (197
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used as is, it is usually chemically sensitized before use. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing complex 1!2 compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of log silver to 10 g/bo.

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

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

Organic compounds that can be used to form the organic radical oxidizing agents described above include U.S. Pat.
There are henzotriadules, 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-113235, and silver acetylene described in JP-A-61-249044. Two or more types of organic silver salts may be used in combination.

The above i-containing silver salts have the following content per mole 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 organic silver salt is 5 (lag to 10 g) in terms of silver.
/Po is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RD 17
643 (1'178), pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds described in JP-A-59-111636. and metal salts thereof, acetylene compounds described in JP-A-62-87957, and the like.

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

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

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

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. , No. 615, 641, JP-A-63-23
145 etc.).

These enhancing dyes may be added to the emulsion during or before or after chemical ripening.
It may be added before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666, and the amount added is generally about 10-s to lo-2 mol per mol of silver halide.

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, transparent or translucent hydrophilic binders are preferred, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, dextran, pullulan, etc.
) M tjl and natural compounds such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers,
Other synthetic polymer compounds may be mentioned. In addition, super absorbent polymers described in JP-A No. 62-245260, i.e., homopolymers of vinyl monomers having -COOM or -sO,M (M is a hydrogen atom or an alkali metal), or these vinyl monomers together or other Copolymers with vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel L manufactured by Juju Chemical Co., Ltd.)
-58) 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 delicate water, the use of the above-mentioned super absorbent polymer allows rapid absorption of water. Furthermore, 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 re-transferred from the dye-fixing material to other materials after transfer.

In the present invention, the amount of binder applied is 2 per tnt.
The amount is preferably 0 g or less, particularly 10 g or less, and 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 stabilizing fragmentation, preventing curling, preventing adhesion, preventing film cracking, and preventing 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 in the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used in the back layer, curling can be prevented. is obtained.

The diffusible reducing agent used in the present invention is a compound that has the ability to develop silver halide and is likely to migrate between coated layers. A diffusible reducing agent is a compound that develops silver halide to become an oxidized form, and this oxidized form undergoes a coupling reaction with a dye-donating compound (color developing agent), or the oxidized form directly or electronically reacts with a dye-donating compound. Any compound (electron transfer agent) that can be cross-oxidized via a diffusion-resistant reducing agent called a donor can be used. Useful reducing agents include dihydroxyhenzenes, catechols, pyrogallol, 3-virapritones, p-phenylenediamines, ρ-aminophenols, sulfonamidophenols, hydrazones, etc. Specific examples include: , U.S. Patent No. 4,500
．． 626 No. 49-5041jl, same No. 4.483.
Columns 30-31 of No. 914, Nos. 4330 and 617,
No. 4.590.152, pages (17) to (18) of JP-A-60440335, No. 57-40245, No. 5G-138736, No. 59-178458, No. 5
No. 9-53831, No. 59-182449, No. 59-
No. 182450, No. 60-119555, No. 60-1
From No. 28436 to No. 60-128439, No. 60
-198540, 60-181742, 61-
No. 259253, No. 62244044, No. 62-13
] No. 253 to No. 62-131256, there are reducing agents and reducing agent precursors described in European Patent No. 220.74662, No. 78 to gB-H.

A particularly preferable diffusible reducing agent is a compound represented by the following --shell formula [XI] or [X-[).

(X-1) H (X-n) In the formula, Ro represents an aryl group.Q)l, R32
R3ff, R14, Rus 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 these may be the same or different.

Examples of the aryl group represented by Ro in general formulas [X-1] and (X-11) include phenyl group, naphthyl group, tolyl group, and xylyl group. It's okay. For example, halogen atoms (chlorine atoms, bromine atoms, etc.), amino groups, alkokino groups, aryloxy groups, hydroxyl groups, aryl groups, carbonamide groups,
Sulfonamide group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group, carboxyl group, sulfo group, aryl group substituted with an alkyl group (methyl group, ethyl group, propyl group, etc.) It may be.

- Stratification (X-1), [X-■]ノR31, R″zR″3
, R3d, RffS, and R36 are alkyl groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.), and these alkyl groups include hydroxyl group, amino group, etc. , a sulfo group, a carboxyl group, etc. Further, as the aryl group, a phenyl group, a naphthyl group, a xylyl group, a tolyl group, etc. can be used. These aryl groups include halogen atoms (chlorine atoms, bromine atoms, etc.),
It may be m10 with an alkyl group (methyl group, ethyl group, propyl group, etc.), hydroxyl group, alkoxy group (methquine group, ethquino group, etc.), sulfo group, carboxyl group, etc.

In the present invention, compounds represented by -stratification cx-n] are particularly effective.

General formula [X-[1], R1+, R3N,
Huff and B24 are hydrogen atoms, carbon atoms 1 to 1O
, a substituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group, more preferably a hydrogen atom, a methyl group, a hydroxymethyl group,
A phenyl group or a phenyl group substituted with a hydrophilic group such as a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group.

Specific examples of the compound represented by -stratification (Xn) are shown below.

(X-1) ■ (X-2) ]I (X-6) ■ (X-3) (X-4) (X-53 (X-9) (X-12) ■ (X-43) ■ The compounds of the present invention are also useful in photosensitive materials containing diffusible reducing agent precursors.

A precursor of a diffusible reducing agent does not have a developing effect when the photosensitive material is stored before use, but can be reduced only by the action of an appropriate activator (e.g., base, nucleophile, etc.) or heating. It is a compound that can release a drug.

In particular, the diffusible reducing agent precursor used in the present invention has no function as a reducing agent before development because the reactive functional group of the reducing agent is blocked by a bronzing group, but under alkaline conditions it does not function as a reducing agent before development. Alternatively, since the blocking group is cleaved by heating, it can function as a reducing agent.

Diffusible reducing agent precursors used in the present invention include, for example, 2- and 3-acyl derivatives of l-phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium , calcium, barium, etc.), halogenated acyl 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, indomethyl groups Examples include reducing agent precursors blocked with .

The diffusible reducing agent precursor used in the present invention is a known compound, for example, U.S. Pat.
．． 246,988, 3.295,978, 3,462) 266, 3.586.506, 3,615.439, 3.650.749, No. 4,209,580, No. 4,330.617,
No. 4,310.612, British Patent No. 1, 0237
No. 01, No. 1, No. 231, No. E130, No. L2
April 58,920, No. 1.346.920, Japanese Unexamined Patent Publication No. 1973
No. 7-40245, No. 58-1139, No. 58-11
No. 40, No. 59-178458, No. 59-18244
The developer precursor described in No. 9, No. 59-182450, etc. can be used.

In particular, 1-phenyl-3 described in JP-A-59478-458, JP-A-59482-449, JP-A-59-182450, etc.
-Precursors of biradurijifun are preferred.

The amount of the diffusible reducing agent and/or diffusible reducing agent precursor to be used has a wide range, but is preferably 0.001 mol to 5 mol, more preferably 0.01 mol per mol of silver halide.
mol to 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 a diffusible reducing agent. The electron donor is preferably used in close proximity to the dye-donating compound and is therefore used in the addition stone of the dye-donating compound. More preferably, it is used in the same layer as the dye-providing compound. Electron donors include dihydroxybenzenes, catechols, pyrogallols, sulfonamidophenols, sulfonamide naphthols, etc., each having a TL-resistant group, European Patent Publication No. 220.746 No. 84
Pages 100 to 95, Patent Application No. 1983-97880, No. 62-3
Examples include reducing agents and/or their precursors described in No. 01887 and the like. Further, a compound of the same type as the compound represented by the general formula (V) or (Vl) 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 layers of the light-sensitive material by a method similar to the above-described method for dispersing the compound of the present invention.

Examples of the reducible dye-providing compound used in the present invention include compounds represented by the following stratification (C).

- Layer formation (C) PWR (Time) T-Dye Here, PWR, Time, and t have the same meanings as in general formula [1] (including preferred examples), and ye refers to the dye or dye precursor. represent.

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

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. Dye-providing compounds described in can also be used.

υNtlL+J:+s(nJ CI(.

CI6H:iff [, Q1 L-1JNl11. ．． 1 bI%33(n)SO2C1
13 Each of these compounds can be synthesized 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/po, preferably 0.1 to 3 mmol/po.
The dye-donating substances having a range of 0 mmol/rrr can be used alone or in combination of two or more.

In addition, in order to obtain an image of black or a different hue, for example, cyan,
At least one magenta and yellow dye-providing substance
It is also possible to use a mixture of two or more dye-providing substances that release mobile dyes having different hues, such as by mixing each species in a layer containing silver halide or in an adjacent layer.

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, Japanese Unexamined Patent Application Publication Nos. 59-83154 and 59-83154,
No. 178451, No. 59-178452, No. 59-1
No. 78453, No. 59-178454, No. 59-IT
8455, 59-178457, etc., if necessary, at a boiling point of 50°C-16.
It can be used in combination with a low boiling point organic solvent at 0°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
L is 10 g or less, preferably 5 g or less. In addition, l c (hereinafter, furthermore, 0.
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
The surfactants listed on pages (37) to (3rd) of No. 157636 can be used.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. Specific compounds that are preferably used are described in U.S. Patent No. 4.5.
No. 00,626, No. 51-52 (fund).

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in US Pat. No. 4,500,626, No. 5711II 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. 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.

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent may be used as a plasticizer, a slippery agent, or a peelability improving agent between the light-sensitive material and the dye-fixing material. Specifically, JP-A No. 62-253159, page (25) and 6
There is one described in No. 2-245253.

Furthermore, various silicone oils (
From dimethylsilicone oil to trimethylsiloxane, there are various types available! All silicone oils up to modified silicone oils with s groups introduced can be used. An example of this is [Modified Silicone Oil] published by Shin-Etsu Silicone.
Various modified silicone oils described in technical information J4P6-18B, especially carboxy-modified silicone (trade name X-22
-3710) etc. are effective.

Also, Japanese Patent Application Laid-Open No. 62-215953, Japanese Patent Application No. 62-236
The silicone oil described in No. 87 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 gold i-complexes.

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

As ultraviolet absorbers, Henztriagul compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-46-2784, etc.), and other JP-A-54-48535, JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, 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
4.195 No. 3-8Ilj! , Japanese Patent Publication No. 62-1747
No. 41, No. 61-88256, pages (27) to (29),
Patent application No. 62-234103, No. 62-31096,
There are compounds described in No. 62-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

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 whitening agent may be used in the photosensitive material or dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. Examples include, Veenkataraman49'T
he Chemistry of 5yntheLic
Dyes J Volume V Chapter 8, JP-A-61-14375
Examples include compounds described in No. 2 and the like. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, hendioxazolyl 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 US Pat. No. 4. (Examples include hardening agents described in Japanese Patent Application Laid-Open No. 116655-1982, No. 62-245261, No. 61-18942, etc.).More specifically, aldehyde-based hardening agents are mentioned. agents (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-ethylene-bis(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (compounds described in JP-A No. 62-234157, etc.).

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved sheerability,
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 oil-based fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Examples include compounds.

A mantle 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. 62410 of benzoguanamine resin beads, polycarbonate resin beads, As resin beads, etc.
There is a compound described in No. 065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61-
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 includes the promotion of the redox reaction between the silver salt oxidizing agent and the reducing agent, and the promotion of the redox reaction between the silver salt oxidizing agent and the reducing agent. It has functions such as promoting reactions such as production 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. They are classified into precursors, nucleophilic compounds, high-boiling solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substances 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 base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines through intramolecular nucleophilic substitution reactions, 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, combinations of poorly soluble metal compounds and compounds capable of complexing reaction with metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

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

The development stopper referred to 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) - (
It is described on page 32).

As the support for the photosensitive material and dye-fixing material of the present invention, materials that can withstand processing temperatures are used. , polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (e.g. triacetyl cellulose) or films containing pigments such as titanium oxide, and film synthesis made from polypropylene. Paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper,
Baryta paper, coated 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 support described on page 1) can also be used.

The surface of these supports may be coated with a wood-philic binder, a semiconductive metal oxide such as alumina silica or tin oxide, or an antistatic agent such as a carbon blank.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which the original image is scanned and exposed through a slit or groove using an exposure device, etc. A method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There is a method of outputting the image to an image display device such as a luminescence display or a plasma display and exposing it 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.
26th issue 56+li! Using the light source described in I, it is possible to:

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 decentralization and electric field that appears when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), /X lithium oxide, BaB! Inorganic compounds such as On,
Urea derivatives, nitroaniline derivatives, e.g. nitropyridine-N-oxide derivatives such as 3-methyl-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 optical waveguide type, fiber type, etc. are known, and both are useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image 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 4 may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1-145544 You can use the information listed on your monthly statement, etc. Note that these conductive layers also function as antistatic layers.

The power 11 heat temperature in the heat development process is about 80'C to about 250°C.
It can be developed at 'C, but especially about 80'C to about 180°
C is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular 50°
More preferably, the temperature is 10'C or higher and about 10'C lower than the temperature in the heat 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
As detailed in No. 56, etc., a small amount of 8 medium (especially water)
Also useful is a method in which development and transfer are performed simultaneously or sequentially by heating in the presence of. In this method, the heating temperature is preferably 50° C. or higher and below the boiling point of the solvent. For example, when the solvent is water, it is preferably 50° C. or higher and 100° C. or lower.

Examples of 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 (
Examples of these bases include those described in the section of image formation accelerators. 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 may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Further, the solvent can be used by being incorporated in the photosensitive material t4, 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 hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. The layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, stylamides, imides, alcohols, 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. , passing through a high-temperature atmosphere, etc.

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 apparatuses can be used to process the photographic elements of the present invention.6 See, for example, JP 59-75247;
No. 59-177547, No. 59-181353,
Apparatuses described in Japanese Utility Model Publication No. 60-18951, Utility Model Application Publication No. 62-25944, etc. are preferably used.

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

A well-stirred gelatin aqueous solution (20 g of gelatin, Ig of potassium bromide, and 0 ff of water in 800 mff of water)
Add 0.5 g of CHs) as(C11
1 and (nl) solutions were added simultaneously at equal flow rates over 30 minutes. In this way, a monodisperse silver bromide emulsion was prepared in which a dye having an average grain size of 0.42 was adsorbed.

After washing with water and desalting, add 20g of lime-treated ossein gelatin and adjust pll to 6.4 and pHg to 8.2.
Incubate at ゛C, add 9.5 kg of sodium thiosulfate and 0.0 kg of chloroauric acid.
01% aqueous solution 6ml, 4-hydroxy-6-methyl 1.
3. Add 3a, 7-chitrazaindene 190a+g,
I underwent chemical exacerbation for 45 minutes. The yield of emulsion was 635 g.

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

A well-stirred aqueous solution (gelatin 2 in 730 d of water)
0mg, potassium bromide 0.30g, sodium chloride 6g
and 60.0°C by adding 0.015g of the following chemical A
The following (1) 1 and (El)? ffl was simultaneously added at equal flow rates over 60 minutes. (1) After the addition of the solution, add the following methanol solution of sensitizing dye B (III
) solution was added. In this way, the average particle size is 0.4
A monodispersed cubic emulsion with dye 5-adsorbed was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting pAg to 7.8, chemical sensitization was performed at 60.0°C. The chemicals used at this time were 1.6 cm of triethyl 1,000 urea and 1.6 cm of 4-hydroxy-6-methyl. 33a,
The trajectory time was 55 minutes with 100 mg of 7-chitrazaindene. The yield of this emulsion was 635 g.

Chemical A Sensitizing Dye B Next, how to prepare the emulsion (I[I) for the fifth layer will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide and 80 (CHg) in 80 ml of water)
The following solution (1) and (I
I)/iI was added simultaneously over a period of 30 minutes. Thereafter, the following solutions (I[[) and (IV)] were simultaneously added over 20 minutes. After addition, potassium iodide 1% water? 30 (C) of liquid 8 was added, and then liquid 8 containing 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 the pH to 6.2) and the pAg to 8.5, followed by sodium thiosulfate and 4-hydroquine-6-methyl 1. 3.
3a,7-thitrazaindene was optimally chemically amplified (8) by adding chloroauric acid. In this way, the average particle size was 0.54
600 g of a 5-monodispersion octahedral silver iodobromide emulsion was obtained.

Dye C Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Weigh out 18 g of yellow dye-donating substance (1), 12 g of electron donor (1) 1, and 9 g of high-boiling organic solvent (1) 0, add 46 ml of ethyl acetate, and heat to about 60°C)
8 to obtain a homogeneous solution. This melt is a 10% solution of lime-treated gelatin? &100g, 60cc of water and 1.5g of sodium dodenruhenzenesulfonate, and then mixed with a homogenizer for 10 minutes at 11,000 cc.
Dispersed at 0 rp. This dispersion is called a yellow dye-providing substance dispersion.

The dispersion of magenta and cyan dye-providing substances is similar to the yellow dye-providing substance, magenta dye-providing substance <2)'', or cyan dye-providing substance f (3
)”.

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

Table 1 (continued 2) Support (polyethylene terephthalate; thickness 100-)
Surface activated (1) 0 Aerosol OT High-boiling organic compound (XI) Tricyclohexylphosphate hardener (1) * 1, 2-bis(vinylsulfonylacetamido)ethane Table 1 (Continued 1) Yellow dye Donor substance π11" Dye-fixed powder 4R 1 Structure The reducing agent (1) was dispersed and added to the polymer (1) 1 in the following manner.

Authorizing agent (]) 815g and polymer (1)” 1.5g
was dissolved in 40 #l of ethyl acetate at about 60°C to form a homogeneous solution.

This solution and 100 g of a 10% aqueous solution of lime-processed gelatin
and surfactant (3) 5% aqueous solution of 8 f&12,6
ml and then stirred and mixed with a homogenizer for 10 minutes io, oo.

Dispersed with rpII.

Next, we will discuss how to make the dye fixing material.

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

Silicone oil 1 Surfactant 1 Aerosol OT Surfactant 1 CaF+ySO*NCHtCOOK H3 Polymer 1 Mordant 1 Dextran (molecular weight 70,000) High boiling point solvent Luofos 95 (manufactured by Ajinomoto ■) (Tzusu IUQ J Next The development inhibitor precursor shown in Table 2 was added to the second and fourth N of the photosensitive material 101 at a molar ratio of 10% to the reducing agent (1) 9, respectively, to obtain the photosensitive materials 102 to 105.
It was created. For comparison, the development inhibitor Precursor AF
Photosensitive material 106.-10 or AP-13 was added to the first layer, third layer, and fifth layer, respectively, at 0,402 mmol/po, 0.02 mmol/po, and 0.03 mmol/po.
107 was created.

In addition, development inhibitor precursor AF-13 and AF-
19 was ground in a mill and added as a fine particle dispersion with an average particle size of 0.2-, other development inhibitor precursors were dissolved together with reducing agent (1) 1 or each dye-donating substance,
It was added as a co-emulsified dispersion.

Further, for comparison, a photosensitive material 10B was prepared by adding a development inhibitor having the following structure to the second layer and the fourth layer in a molar ratio of 1% to 9 of the reducing agent (1).

A tungsten light bulb is used for the color photosensitive materials 101-108 having a multilayer structure, and the density of B and G is continuously changed.
, R and Gray color separation filters at 500 lux for 1 second.

This exposed light-sensitive material was immersed in water for 5 seconds, passed between a pair of rubber rollers to remove excess water, and then stacked on dye-fixing material R-1 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 75°C. When it was then peeled off from the dye-fixing material, clear images of blue, green, red, and gray were obtained on the fixing material, corresponding to the B, G, R, and gray color separation filters.

Table 2 shows the results of measuring the maximum density (D, , ) and minimum 4 degrees (D, i, , ) of each color of cyan, magenta, and yellow in the gray part.

Table 2 shows that in the case of the present invention in which a development inhibitor precursor was added to the intermediate layer, Djorn hardly increased. In contrast to the increase in X, in photosensitive materials in which a development inhibitor precursor was added to the emulsion layer (Nα 106.107) and in photosensitive materials in which a development inhibitor was added to the intermediate layer (Nα 108).

,,Dl,7 increased with an increase in l.

Example 2 Reducing agent (1) 8 in the intermediate layer was replaced with the following reducing agent (2) 0 or reducing agent (3) 9 in equimolar amounts, and further polymer (1)
) 0 is replaced with the high boiling point organic solvent (1) 0 in equal weight, and the photosensitive materials 201 to 208 have the same structure as in Example 1 (reducing agent (
2 Bi) or photosensitive materials 301 to 308 (reducing agent (3
) 0 usage) was created.

Reducing agent (3) 0 When the same dye fixing material R-1 as in Example 1 was used and treated in the same manner, D sin hardly increased in the case of the present invention in which a development inhibitor precursor was added to the intermediate layer. In contrast, in light-sensitive materials added to the emulsion layer and in light-sensitive materials in which a developing agent (■) was added to the intermediate layer, as D w x increase +
3+1 was seen.

Example 3 A color photosensitive material 401 having a multilayer structure shown in Table 3 was prepared using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as those used in the photosensitive material 101 of Example 1.

Note that the same additives as in Example 1 were used unless otherwise specified.

The organic silver salt emulsion was prepared as follows.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed with 10 g of 0.1% sodium hydroxide aqueous solution.
00aj! and 200% of ethanol. This solution was kept at 40°C and stirred. Add 4.5 ml of silver nitrate to this solution.
A solution of 200 g of water dissolved in 200 g of water was added over 5 minutes.

Excess salt was then removed by sedimentation. Thereafter, the pH was adjusted to 6.3 to obtain 1300 g of an organic silver salt dispersion.

Further, in the photosensitive material 401, the development inhibitor precursor shown in Table 4 was added to the second layer and the fourth layer at a molar ratio of 10% to 1 part of the reducing agent (1), respectively.
403 was created. For comparison, 0 of the development inhibitor precursor AF13 was added to the first layer, third N, and fifth layer.
．． A photosensitive material 404 was prepared by adding 0.3 mmol/if. Note that the development inhibitor precursor is reducing agent (1) 1
Alternatively, it was dissolved together with each dye-providing substance and added as a co-emulsified dispersion.

Table 3 (continued 1) 3 (continued 2) Support (polyethylene terephthalate: thickness 100μ)
Thermal melting x1) 8 Hensensulfonamide base precursor (1) 0 4-Chlorphenylsulfonylacetate guanidine Next, the method for producing the dye fixing material R-2 will be described.

Dissolve 10 g of poly(methyl acrylate-N,N,N-)methyl-N-vinylbenzylammonium chloride (molar ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) in 200 d of water,
It was uniformly mixed with 100 g of 10% lime-treated gelatin. A hardening agent was added to this mixed solution, and the mixture was uniformly applied to a wet film thickness of 90I1 m on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying this sample, it is used as dye fixing material R-2 having a mordant layer.

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

After 20 mft of water per layer was supplied to the film side of the dye fixing material R-2, the heat-treated photosensitive materials were stacked on the fixing material so that the film surfaces were in contact with each other.

After that, it was placed in a laminator heated to 80°C at a linear speed of 12ml.
/sec, and then peeling off both materials, to obtain blue, green, and red spectral durams corresponding to the wavelengths on the dye-fixing material. Table 4 shows the results of measuring the density of cyan and magenta in the blue light area, cyan in the green light area, magenta and yellow in the yellow red light area.

From Table 4, it was found that in the present invention in which a development inhibitor precursor was added to the intermediate layer, color reproducibility was improved and high density was obtained. It should be noted that the photosensitive material 404 in which a development inhibitor precursor was added to the emulsion layer caused color turbidity.

Continued (Ho Positive book 1. IH Cow Lift R 1986 Patent Application No. 262911 Heisei! February 77th 2) Name of the invention

Claims (2)

[Claims] (1) A heat-developable color photosensitive material having on a support at least a photosensitive silver halide, a binder, a diffusible reducing agent, and a reducible dye-providing compound that releases a diffusible dye when reduced. A diffusion-resistant development inhibitor precursor having at least two photosensitive layers having different properties and capable of releasing a diffusion-resistant reducing agent and a diffusible development inhibitor between the two photosensitive layers. A heat-developable color photosensitive material, characterized in that it has a layer containing at least one type of each layer. (2) A method for forming a color image, which comprises heat-developing the heat-developable color photosensitive material according to claim 1 after or simultaneously with image exposure.