JPH01145652A - Thermally developable color photosensitive material - Google Patents

Abstract

PURPOSE:To reduce the stain of a transferred positive image and to obtain a stable positive image by adding a specified compd. to a thermally developable color photosensitive material having a reducible dye providing compd. CONSTITUTION:A compd. represented by formula I is added to a thermally developable color photosensitive material having at least a photosensitive silver halide emulsion, a binder, a reducing agent or a precursor thereof and a reducible dye providing compd. which releases a diffusible dye on being reduced on the support. In formula I, RED is a redox nucleus and atomic group capable of releasing -(TIME)n-FA on being oxidized during development, TIME is a timing group combining with RED through S, N, O or Se, n=0 or 1 and FA is a group which functions as a fogging agent or a development accelerator for silver halide after release from -(TIME)n-FA. The stain of a transferred positive image is remarkably reduced and a high quality positive image is obtd.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a heat-developable color photosensitive material.
The present invention relates to a heat-developable color photosensitive material that can obtain positive color images with a high temperature of 11 degrees and low stain.

(Prior art and its problems) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (Published by Corona Publishing Co., Ltd., 2012) 2
4t, pages 2 and 3, US Pat. No. AZOOT2, etc.

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

For example, US patent! ! The Tata O has a so-called DRR.
A reducing agent or its precursor is coexisted with an oxidized compound that does not have the ability to release chemical compounds, and the reducing agent is oxidized according to the exposure amount of silver dihalide by thermal development, and the remaining unoxidized reduction is removed. A method has been proposed in which a diffusible dye is released by reduction with an agent. Also, European Patent Publication-2074
L4 issue, Public Technical Report 17-4/Tata (Volume 1 Coco Issue) K
is a compound that releases a diffusible dye by a similar mechanism.
A heat-developable color light-sensitive material is described that uses 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).

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 in transferred positive images. .

In order to suppress staining in a photothermographic material for forming positive images using such a reducible dye-donating compound, a diffusible electron transfer agent is used in addition to a diffusion-resistant electron donor as a reducing agent. is effective, but it is still not at a sufficient level. Further, there is a problem in that the stain tends to change due to changes in development temperature and development time.

(Object of the Invention) An object of the present invention is to reduce the staining of a transferred positive image of a heat-developable color light-sensitive material using a reducible dye-providing compound. Another object of the present invention is to provide a heat-developable color photosensitive material capable of producing a stable positive image despite fluctuations in development temperature and time.

(Structure of the Invention) An object of the present invention is to provide at least a photosensitive silver halide emulsion, a binder, a reducing agent or a precursor thereof, and a reducible dye-donating compound that releases a diffusible dye when reduced, on a support. This could be achieved by a heat-developable color photosensitive material which further contains a compound represented by the following general formula [I].

General formula (1) % formula %) In the formula, RED means a redox mother nucleus, and is an atomic group that makes it possible to release fi-(TIME)n-FA by being oxidized during development processing. be.

TIME represents a timing group linked to ED with S, N, O or 8e, and n represents O or an integer of /.

FA represents a group that functions as a fogging agent or a development accelerator for silver thihalide released from -(TIME)n-FA.

The compound of the above general formula [1] of the present invention significantly reduces the staining of transferred positive images of heat-developable color photosensitive materials using reducible dye-providing compounds, resulting in high-quality positive images. .

In the general formula (1), FA represents a so-called fogging agent or development accelerator that acts on silver halide grains during thermal development to generate fog nuclei capable of initiating development. The FA is preferably a group that acts reductively on silver halide grains during development to produce fog nuclei, or acts on silver halide grains to produce silver sulfide nuclei, which are fog nuclei capable of initiating development. This can be cited as an example.

A preferable group as FA is a group containing a group having adsorption properties to silver halide grains, and can be used as described below.

AD-(L)m-X AD represents a group having adsorption properties to silver halide, L represents a divalent group, and m represents O or/. X
represents a reducing group or a group capable of producing silver sulfide by acting on silver halogenide. However, if X is the latter, it may also have the function of AD, so AD-(L)m- is not necessarily required in this case.

When FA is a group represented by AD-(L)m-x,
The bonding position with TIME and RED is AD-(L)m-x
It can be at any position.

In the general formula (IN, -(TIME) n-FA is
几ED undergoes a redox reaction with exposed silver halide or electron transfer agent radicals and its subsequent reaction.
It is coupled to a device consisting of RED.

In general formula (1), the group represented by RED is hydroquinone, catechol, O-aminophenol or p-aminephenol, /, 2-naphthalenediol,
/,! -7talediol, /, 2-aminonaphthol, l, has a skeleton of Hiro-aminonaphthol group, and undergoes a redox reaction with exposed silver halide or electron transfer agent radicals, followed by alkaline hydrolysis. -(TIME)n-FA group (the following general formula [■a] ~ (n
f) represents a group that releases (abbreviated as PR).

Specific examples thereof are shown in general formulas (Ila) to (Ilf).

k′ruNH30□-FR In the above formula, R1 is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carb-6-H syl group, sulfo group, sulfonyl group, acyl group, carbo/ represents an amide group, sulfonamide group, hydroxy group, acyloxy group or heterocyclic group, R
If there are two or more 1s, they may be different from each other,
Further, two vic-positions may be bonded to form a benzene ring, a t~7-membered non-benzene hydrocarbon ring, or a j~7-membered heterocycle. FR2 represents an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group.

T1 represents a hydrogen atom or a group capable of being hydrolyzed and separated under alkaline conditions. When there is one T1 in the molecule, they may be different from each other. A typical example of T1 is
Examples include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, and an ogissalyl group.

Preferred specific examples of general formula (Ila) to l1f) are shown below. Note that in each structural formula (old) indicates the position where FR is bonded.

H H H (4) oHoH oH oH oH oH (lO) oH oH oH oH oH oH oH (19) 0 0H Supper H Six-chain H (2B) H 02CH3 5H to t-, timing group given by 1 TIME As for U.S. Patent No. 2.2, No. 6-6, Tokuhan Sho! 7-! As described in No. 6137 etc., it is released from RED by redox reaction and then released from QFA by intramolecular substitution reaction, British Patent Co., No. 07, No. 363, JP-A-17-1996/ JIJJF
No. 77-/1fOJj No. 54-//&P! No. 4, same! 7-! No. 16137, same! ! -20P7Jt,
same! ! - Koori No. 737, 71-. ? 0ri 73♂ issue,
Examples include those that leave the FA by electron transfer via a conjugated system, such as JLR-20-74TO and 5R-21721. These reactions may occur in one step or in multiple steps.

When FA is a group containing AD-(L)m-X, the group capable of adsorbing to the silver halide that is added with AD is nitrogen het-ffi (virol, virol, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), at least 7 nitrogen atoms in the ring and other Heterocycles (oxazole, thiazole, thiazoline, thiazolidine, thiadiazole, benzothiazole,
benzoxazole, benzoselenazole, etc.), heterocycles with mercapto groups (2-mercaptobenzothiazole, --mercaptopyrimidine, λ-mercaptobenzoxazole, l-phenyl-mercaptotetrasol, etc.), chlorinated salts (3 grade amine, pyridine, quinoline,
(benzothiazole, benzimidazole, benzoxazole, etc.), thiophenol thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbic acid, etc.)
It is possible to list things consisting of, etc.

The divalent linking group represented by L in FA includes alkylene, alkenyl group, phenylene, naphthylene, -o-1
-s-1-so-1-so2-1- N -N -, carbonyl, amide, thioamide, sulfonamide, ureido, thioureido, heterocycle, etc.

Examples of the group represented by X include reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine,
/-Phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt.

≠ salts such as ethylene bispyridinium salts (carbazic acid, etc.) or compounds that can form silver sulfide during development (for example, thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, compounds having the structure, etc.). I can do it. Among the groups represented by I can do it.

Furthermore, particularly preferred among FAs are the following general formulas (Io
ta ) and (■b 3).

General formula ('m-a) Female one!8 formula [■b] In the formula, Rz1 represents a haacyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group or sulfamoyl group, R23 represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group; m represents an integer of O-Hiroshi, and when m is 2 or more, R and 3 may be the same or different; Two or more may stick together to form a condensed ring.L has the same meaning as mentioned above, that is, it represents a divalent linking group, and n represents 0 or l.Zl is Represents a monocyclic or fused heterocyclic ring.

Examples of substituents are described in more detail below. R.

As, acyl group (formyl group, acetyl group, propionyl group, trifluoroacetyl group, pyruvoyl group, etc.)
, carbamoyl group (dimethylcarbamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, etc.), ryorylsulfonyl group (benzenesulfonyl Jl), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.) or sulfuryl moyl group (methylsulfuryl group, etc.),
-2 is a hydrogen atom, a hydrogen atom, a trifluoroacetyl group (such as a trifluoroacetyl group), an alkoxycarbonyl group (such as a methoxycarbonyl group), or a carbonyl group (such as a phenoxycarbonyl group).

R23 is a halogen atom (fluorine atom, chlorine atom, etc.), an alkoxy group (methoxy group, methoxyethoxyl group, etc.), an alkyl group (methyl group, hydroquine methyl group, etc.),
Alkenyl groups (allyl groups, etc.), ryoryl groups (phenyl groups, etc.), ryoloxy groups (phenoxy groups, etc.), alkylthio groups (methylthio groups, etc.), arylthio groups (phenylthio groups, etc.), carbonamide groups (acetamido groups, etc.) ) or sulfonamide groups (such as methanesulfonamide groups) are shown in the examples of AD listed below.

An example of the FR compound used in the invention is JP-A-Shoj7-/!
;Or'A! r, 5ter 5Oy-3ri, jter/37otsu 3♂, jter/70g4LO, sameotsu 0
-37ta! Otsu No., Otsu 0-/0702 Ri No.

Special request! ! -23710/etc.

An example of AD is shown below. Free bonds are bonded to -(L)-X and -(TIME)-
nru.

H3 An example of L is shown below.

CH2, CH2CH2, 0CH2.

-0CH2CH2-, -8CH2-, -COO- Examples of X are shown below.

NHNHCHO, NHNHCOCH3.

-NHNH5O2CH3, -NHNHCOCF3.

-N-NHCHO COOC2H5.

-CONHNHCH3, -CONHNH2.

Further, preferred specific examples of FA in general formula (13) are shown below.

C) 12CH2CHO H3 Specific examples of the compound represented by the general formula [I] are shown below, but the present invention is not limited thereto.

:+r.

Usllo t 0H NHNH8O2C2H5 H CH2C:=CH /3 ■ H 3ko0H CH2C=CH J≠ H H L:H2C:=CH The compound of the present invention is disclosed in, for example, JP-A-67-/jOtit-
R issue, Tokukai Sho! ? -/j7tjlr issue and Japanese Patent Application Publication No. 1989
It can be synthesized by a method similar to that described in No.-107022.

FR compounds are, for example, research disclosure (
几search Disclosure ) Magazine & 2
Patents cited in Ko, 33μ (published in 1991.3/month, jON page 314), and US patent #! μ, μ7/.

It can be synthesized by the method described in No.

Moreover, in addition to the above-mentioned compounds of the present invention, so-called DIR compounds may be used in combination. As DIR compounds, those described in Japanese Patent Application Laid-open No.
DIR compounds having a redox core as shown by the symbol -/μO can be mentioned.

The compound of general formula (1) of the present invention may be used in a photosensitive layer, an intermediate layer, a protective layer or other auxiliary layer. Furthermore, when the silver halide emulsion and the reducible dye-providing compound are added to separate layers, it may be used in either of them.

However, it is particularly preferred to add it to layers containing silver halide emulsions. The amount added is 0°00/~ per mole of silver halide! Mol, preferably o, ooz to l,
5 mol, 000 per mol of reducible dye-donating compound
The amount of IN is 0 mol, preferably 0 to 1 mole, preferably 1.117 to 10 mole, preferably no to 10 mole per mole of reducing agent or its precursor.

Further, the compound of general formula (1) of the present invention can also serve as an electron donor.

In the present invention, a reducible dye-providing compound is combined with a reducing agent, a binder, and a silver 10-genide emulsion to form a heat-developable photosensitive layer of 1 unit. The reducible dye-providing compound may be added to the same layer as the silver halide emulsion, or may be added separately to adjacent layers. In the latter case, it is preferable from the viewpoint of sensitivity that the layer containing the reducible dye-providing compound is located below the silver halide emulsion layer.

Normally, in order to reproduce full color, three sets of photosensitive layers with different color sensitivities are provided. For example, there are three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer.
There are combinations of three sets, a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can have various arrangement orders known in conventional color photosensitive materials. Further, each of these color-sensitive layers may be divided into 2# or more, if necessary.

The heat-developable color photosensitive material can be provided with various auxiliary layers such as a frame, an undercoat layer, an intermediate layer, a yellow filter layer, an anti-Norski layer, and a pack layer.

In the present invention, in order to increase the maximum density of the transferred positive image,
A compound that releases a group that functions as a development inhibitor for silver halide upon oxidation during thermal development can be used in combination.

Such compounds are generally known as DIR compounds in the field of photographic materials, and known DIR compounds can also be used in the present invention. For example, in the present invention, examples of the DIR compound include the compounds described in JP-A-62-06-06 Hiroj, pages (9) to (10) and (14c) to (/n).

In addition, in the present invention, in order to increase the maximum density of the transferred positive image and further suppress staining, reduced n is added during the heat development process.
It is also possible to use a compound which releases a group which functions as a development inhibitor for silver halide.

Specific examples of these compounds can be found in European Patent Publication No. 07441
．． Iriko issue, Public branch number r7-6/99, JP-A-42-J
/ Described in No. 1270, etc.

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

The reducible dye-providing compound used in the present invention is as follows.

Preferably, it is a compound represented by the following general formula [L].

PWR-(Time) -Dy e In the formula (L), PWR is reduced by reducing -(Time)
t-])ye represents a t-releasing group.

Time is from PWR -(T im e )1-Dy
represents a group that releases Dye through a subsequent reaction after being released as e.

t represents an integer of O or l.

Dye coats the color casing or its precursor.

First, PWH will be explained in detail.

PWR is based on U.S. Patent μ,/3, No. 312, or U.S. Pat.
Tokukai Akira! Tar/1r1333, 47-r4! μyo3
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 Gu, Ko 3, 10
No. 7, Tokukai Akira! Research Disclosure (i9ru) N5. ? No. 4A02s: As disclosed in JP-A No. 61-21237, an electron-accepting quinonoid center in a compound that eliminates a photographic reagent by an electron transfer reaction within the molecule after being reduced, and its combination with a photographic reagent. It may correspond to a part containing a carbon atom that connects . Tokukai Akira again! t-
74! Ko! No. 30, U.S. Patent II, 31t3,193, Dohiro, 6/ri, rr4! The aryl group substituted with an electron-withdrawing group in the compound whose single bond is cleaved to release the photographic reagent after reduction as disclosed in No. It may correspond to a part containing (atom). It also corresponds to the moiety containing the nitro group in the 2)a compound that releases the photographic reagent after electron acceptance and the carbon atom that connects it to the photographic reagent, as disclosed in U.S. Patent No. 10,223. It may be something that does, or U.S. Pat.
tO, even if it corresponds to the geminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance described in No. 6IO and the moiety containing the carbon atom that connects it with the photographic reagent. Good 6 Matata Tokugan 1986
-5o2-x (x
represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group. A compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule as described in No.
Compounds having a c-x' bond (X/ is synonymous with X or represents -5O2-) and an electron-withdrawing group in one molecule can also be used.

However, in order to satisfactorily achieve the object of the present invention, among the compounds of the general formula CL), those represented by the general formula (LII) are preferred.

General formula (LII) (Time+TDye binds to at least one of R1□, R2, or EAG.

The portion corresponding to PWR in general formula (LH) will be explained.

X represents a group (-N(R3)-) containing an oxygen atom (-0-), a sulfur atom (-8-), or a nitrogen atom.

RR and R3 are groups other than hydrogen atoms, or 1 to 2 Friend simply represents a union.

Groups other than hydrogen atoms replaced by R□, R2, and R3 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, etc. can be mentioned. These groups include those having substituents. A specific example is public branch root 17-. 4/Tata issue pages 2-3
The basis of the description is listed in the left column of the page.

几 and R3Fi are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc. The number of carbon atoms in R1 and R3 is preferably from / to 0.

R2 is preferably a substituted or unsubstituted acyl group or sulfonyl group. The number of carbon atoms is preferably 1-μO.

几1, R, 2, R3 and EAG may be combined with each other to form a ring.

EAG will be described later.

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

General formula [for L] (T im e + TD y e is bonded to at least one of R4 and EAG.

The portion corresponding to PW in the general formula (LIn) will be explained. 0Y is a divalent linking group, preferably -C- or -5O2-. X
has the same meaning as above.

R4 represents an atomic group that is bonded to X%Y to form a monocyclic or condensed heterocyclic ring containing five or more members including a nitrogen atom.

Preferred examples of the portion corresponding to this heterocycle are listed below.

to L G LAtJ EA (i
AG EAG YuG AAL
h■ EAG EAG EAG where R8, R9 and RIO are preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

B 11 represents an alkyl group, an aryl group, an acyl group, or a sulfonyl group.

(Time-)-L)ye is 几8, 几9, B 10 K
They may be combined.

EAG has an aromatic group that accepts and takes electrons from reducing substances and bonds to nitrogen atoms. As EAG, the following general formula (
Groups that are swirled in A) are preferred.

General Formula (A) In General Formula (A), Kan Vn represents an atomic group forming a three to three-person aromatic group together with Z□ and Z2, and n represents an integer from 3 to t.

V3 is -Z3-, ■4 is -Z3-Z4-1■ is -Z-Z-Z5-1 ■6 is -z 3-z 4-z 5-z 6-1V7 is -
z 3-z 4-z 5-z 6-z 7-1V is -Z -Z -Z 5-Z6-Z7-Z8-f. Here, each of Z − Z8 represents Sub, and each Sub is a simple bond (pi bond),
Represents a hydrogen atom or the substituents listed below. Sub may be the same or different, or may be bonded to each other to form a 3- to 3-member saturated or unsaturated carbocyclic or heterocyclic ring.

In general formula (A), the sum of 7, met substituent constant sigma, and V of the substituents is +0.20 or more, more preferably +
0.70 or more, most preferably 10.

Select Sub so that it is equal to or higher than rz.

EAG will be described in more detail.

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group.

Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire compound. Examples of the physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusivity, etc.
It can be used to adjust sublimability, melting point, dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with electrophilic groups, etc.

A specific example of EAG is published in European Patent Publication, No. 2-07μ6A-! It is described on pages 7 to 7.

Time is a timing group having the same meaning as described in the general formula (1) above.

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 be multicolored during development.

Specifically, EP7J, ≠92A, JP-A-Shojter/61
The dye disclosed in No. 0jII can be used.

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 7-67-2 etc. can also be used.

C0NHC16H33(n) CR3 76su/ 碳- 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 0.0j-j mmol/m2, preferably 0.0j-j mmol/m2. /~
It is in the range of 3 mmol/m2.

The dye-donating substances can be used alone or in combination of two or more. Moreover, in order to obtain an image of black or a different hue, JP-A-70-/J Coco! As described in No. 2, for example, cyan, magenta, and yellow dye-providing substances are mixed and contained in a layer containing silver halogenide or in an adjacent layer, for example, to form a movable material having different hues. It is also possible to use a mixture of two or more kinds of dye-providing substances that release a sex dye.

The reducing agent used in the present invention is European Patent Publication No. 2207≠JAJ
No., published branch root r7-6/Tata, JP-A-62-2/jλ7
Examples include compounds described in No. 0 and the like. It is preferred to use a combination of an electron transfer agent and an electron donor as the reducing agent. In this case, particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formulas (1) and/or (n). Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula (C) or CD).

In the formula, A1 and A2 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophile.

Here, the nucleophile is OHe, Roo(R;
alkyl groups, aryl groups, etc.), anionic reagents such as hydroxamic acid anions So3''e, l- or secondary amines, hydrazine, hydroxylamines, Z alcohols, thiols, etc. with unshared electron pairs. Examples include compounds.

A1. Preferred examples of A2 include a hydrogen atom, an acyl group,
Alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoryl group, dialkylphosphoryl group, or JP-A-Sho! It may be a protecting group disclosed in the same No. 7037 and the same No. 20101, and A1 and A2 may be bonded to each other with R1, R2, R3 and R4 to form a ring, if possible. Also good. Further, A 1 s A 2 may be the same or different.

R1, R2, R3 and R4 are each a hydrogen atom, an alkyl group (optionally substituted alkyl group, e.g. methyl group, ethyl group, n-methyl group, cyclohexyl group, n-octyl group, allyl group, 5ec-octyl group) , tert-
Octyl group, n-dodecyl group, n-tadecyl group, n
-hexadecyl group, tert-octadecyl group, 3-hetesadecanoylaminophenylmethyl group, ≠-hexadecylsulfonylaminophenylmethyl group, 2-ethoxycarbonylethyl group, 3-carboxypropyl group, N-
Ethylhexyldecylsulfonylaminomethyl group, N-methyldodecylsulfonylaminoethyl group); Aryl group (optionally substituted aryl group, e.g. C, phenyl group%
3-hexadecyloxyphenyl group, 3-methoxyphenyl group, 3-sulfophenyl group, 3-chlorophenyl group, cocarpoxyphenyl group, 3-dodecanoylaminophenyl group, etc.); alkylthio group (optionally substituted) Alkylthio groups, such as n-butylthio group, methylthio group, tert-octylthio group, n-dodecylthio group, cohydroxyetherthio group, n-hexadecylthio group, 3-ethoxycarbonylzolopiotheo group, etc.)
;Arylthio group (optionally substituted arylthio group, e.g. phenylthio group, Hiro-chlorophenylthio group, λ
-n-octyloxy-j-1-duterphenylthio group, Hiro-dodecyloxyphenylthio group, Hiro-hexadecanoylamine phenylthio group, etc.); Sulfonyl group (optionally substituted aryl or alkylsulfonyl group, etc.); t hamethanesulfonyl group, butanesulfonyl group, p
-toluenesulfonyl group, ψ-dodecyloxyphenylsulfonyl ts, tt-acetylaminophenylsulfonyl group, etc.); sulfo group: halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom); cyano group; carbamoyl group (substituted Carbamoyl group that may be substituted, such as methylcarbamoyl group, diethylcarbamoyl group,
-(2,Hiro-di-t-inchylphenyloxy)furobylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octyl group (moyl group, etc.); sulfamoyl group (optionally substituted sulfamoyl group, e.g. diethyl sulf famoyl group, di-n-octylsulfamoyl group, n-hexadecylsulfamoyl group, 3-is
.

-hexadecanoylaminophenylsulfamoyl group, etc.); amide group (optionally substituted amide group, acetamido group, 1so-butyroylamino group, ≠-tetradecyloxyphenylbenzamide group, 3-hexadecanoylamino group) benzamide group, etc.); imide group (optionally substituted imide group, such as succinimide group, 3-laurylconophosphate imide group, phthalimide group); carboxyl group; sulfonamide group (optionally substituted sulfonamide group, etc.); A group such as a methanesulfonamide group, an octanesulfonamide group, a hexadecanesulfonamide group, a benzenesulfonamide group, a luenesulfonamide group, and a Hiro-lauryloxybenzenesulfonamide group.

However, the total carbon number of R1-R4 is r or more. Furthermore, in general formula (C), R1 and R2 and/or R
and R are R1 and R2, R2 and R in general formula [D]
3 and/or R3 and R4 may be bonded to each other to form a saturated or unsaturated ring.

Among the electron donors represented by the general formula [C] or [D], those in which at least two of R-R are substituents other than hydrogen atoms are preferred.

Particularly preferred compounds are those in which at least one of R1 and R2 and at least one of R3 and R4 are substituents other than hydrogen atoms.

A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination. Further, the electron donor may be the same compound as the reducing substance of the present invention. All specific examples of electron donors are listed, but the invention is not limited to these compounds.

(ED-/) (ED-2) (ED--?) (ED-≠) (ED-j) (ED-t) (ED-7) (ED-r) (ED-ta) (ED-to ) H (ED-//) (ED-/2) The amount of the electron donor (or its precursor) to be used varies within a wide range, but is preferably 000 O per 7 moles of the positive dye-donating substance.
1 mole~! A preferred range is on the order of 0 mol, especially O01 mol. Also/・0.001 mol to j mol, preferably o, oi mol to 1 mol per 1!1 mol of rogogenation
．． It is 5 moles.

Any compound can be used as long as it is oxidized by the silver halide used in combination with these electron donors and its oxidized form has the ability to cross-oxidize the electron donor, but Preferably something that is movable.

A particularly preferred ETA is a compound represented by the following formula CX-/:l or [X,2].

(X-I) (X-11) In the formula, R represents an aryl group. R, R1R, R, R and R are hydrogen atoms,
It represents a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and these may be the same or different.

- The aryl group represented by R in the formula [X-l1l, (X-II) includes, for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and the like. These groups may be substituted. Inverted halogen atoms (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, It may also be an aryl group substituted with a carbamoyloxy group, carbonate group, carboxyl group, sulfo group, alkyl group (methyl group, ethyl group, propyl group, etc.).

- R, R, R13 of formula [X-11, [:X-11],
The alkyl group represented by R14, R15 and R16 is
An alkyl group having a carbon number of 1 to IO (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), and these alkyl groups may be substituted with a hydroxyl group, an amine group, a sulfo group, a carboxyl group, etc. . Further, as the aryl group, phenyl group, naphthyl group, xylyl group, tolyl group, etc. can be used. These aryl groups are
Substituted with I.logen atoms (chlorine atom, bromine atom, etc.), alkyl groups (methyl group, ethyl group, propyl group, etc.), hydroxyl group, alkoxy group (methoxy group, ethoxy group, etc.), sulfo group, carboxyl group, etc. Good too.

In the present invention, a compound represented by formula (X-II) is particularly preferred. -Formula (X-n:l, R
11, R12, R13 and R14 are preferably a hydrogen atom, an alkyl group having -10 carbon atoms, a substituted alkyl group having -10 carbon atoms, and a substituted or unsubstituted AIJ-al group,
More preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group, a hydroxyl group, an alkoxy group, a sulfo group,
It is a phenyl group substituted with a hydrophilic group such as a carboxyl group.

Specific examples of compounds represented by formulas [X-1] and [:X-II] are shown below.

(X-/) (X-2) (X-3)
(X-t) (X-≠) (X-7) (X-3> (X-Ir) (X-ta) (X
-10) The ETA precursor used in the present invention does not have a developing effect during the storage of the photosensitive material before use, but it can be treated with an appropriate activator (e.g., base, nucleophile, etc.) or heating. This is the first compound that can release ETA.

In particular, the ET human precursor used in the present invention has a reactive functional group of ETA blocked with a blocking group.
Although it does not function as an ETA before being a toy, it can function as an ETA because the si-blocking group is cleaved under alkaline conditions or when heated.

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

The ETA precursor used in the present invention is a known compound, such as U.S. Pat. No. 7J7.704c, U.S. Pat. Oyumi, Ri Ir No. 3, 2 Ri J, No. 971, No. 3. ≠62.21. No. 3
, tJl, No. 106, same No. J, t/j, 3rd issue,
Same 3rd. tjO, 7 hiro issue, ko 0ri, rro issue, 330, A/7 issue, 4th issue (, 310, t
/2, British Patent No. 1.023.70/, British Patent No. 1.2
3/.

No. 130, No. 1.211.921A, No. 1゜3 Hirot, No. 720, JP-A-57-Hiro02-Hiro5, No. 11-/
/ Jri issue, same! Same as r-//ll-0? -/7
r 4Cj No. 1, same! ? The developer precursor described in No. -/l'21AII-9, No. 1/rλ'AjO, etc. can be used.

In particular, the /-phenyl-
Precursors of 3-pyrazolidinones are preferred.

In the present invention, the combination of electron donor and ETA is preferably incorporated into the heat-developable color photosensitive material. Electron donors, ETAs, or their precursors can be used in combination of λ or more, and can be used in emulsion layers (blue-sensitive layer, green-sensitive layer, red-sensitive layer, infrared-sensitive layer, ultraviolet-sensitive layer, etc.) in light-sensitive materials. It can be added to each emulsion layer or only to some emulsion layers.
Further, it can be added to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, retention layer, etc.), or even to all layers. The electron donor and ETA can be added to the same layer or to separate layers. Additionally, these reducing agents can be added in the same layer as the dye-donating substance or in a separate layer; however, it is preferable that the diffusion-resistant electron donor be present in the same layer as the dye-donating substance. preferable.

ETA can be incorporated into the image-receiving material (dye fixing layer), or if a small amount of water is present during thermal development, it can be dissolved in this water. The preferable amount of the electron donor, ETA or its precursor used is 0.0/~10 mol in total per 1 mol of the dye-donating substance, preferably tL<uO, 7~
3 mol, halogen (t [0.00 in total per 1 mol)
/-1 mol, preferably o, oi~/,! It is a mole.

Further, the amount of ETA is to mol % or less, preferably aO mol % or less of the entire reducing agent. When ETA is dissolved in water and supplied, the concentration of ETA is lo-4 mol/l-1 mol/
l is preferred.

In order to introduce the compound of general formula (1) of the present invention, a reducible dye-donating substance, an electron donor, an electron transfer agent or their precursor, and other hydrophobic additives into a hydrophilic colloid chamber, Boiling point organic solvents such as phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. benzoic acid) octyl), algylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimenoic acid esters (e.g. tributyl trimesate), patent application Sho A/-23/! Carboxylic acids described in JP-A No. 00, JP-A No. 711/-rI, JP-A No. 711/-rI, JP-A-J
Tar/7rlAj No. 2, Tar/71 Hiroj No. 3, Same j
Tar 17♂ Hiroj Hiro issue, same! 9-/7111-j3, the method described in U.S. Pat. , lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After dissolving in methyl cellulose acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point solvent may be mixed and used.

Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like, if necessary, before use. The amount of high boiling point organic solvent is IOf for the dye-donating substance/7 used.
Hereinafter, preferably J' is as follows. Also, the diffusion-resistant reducing agent/f is 52 or less, preferably 2? It is as follows. Furthermore, it is appropriate that the amount of high boiling point organic solvent/2 to binder/2 is below, preferably below 0.39, more preferably below 0M. Also, Tokuko Shoj/-Jri No. 113, Tokukai Sho!
The dispersion method using a polymer described in ;/-j Tata≠3 can also be used. In addition, it can be directly dispersed in an emulsion, or it can be dissolved in water or alcohol and then dispersed in gelatin or an emulsion.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above. (For example, JP-A No. 17≠130, JP-A No. 13-1
0 Core No. 33, Japanese Patent Application No. 62104112, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, those listed as surfactants in pages (37) to (3g) of JP-A No. 7A/J7AjA can be used.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

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 directly combined with a nucleating agent and an optical coupler. Used as a reversal emulsion. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.
Silver halide emulsions may be monodisperse or polydisperse (monodisperse emulsions may be mixed and used)6 Grain sizes are 0.1 to 2
[mu], particularly preferably 0.2 to 1.5 [mu].The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high 7 spectral ratio, or any other form.

Specifically, U.S. Pat. No. 4,500,626, column 50;
Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), No. 4,628.021, JP-A-60-196748, No. 60-192937
Any of the silver halide emulsions described in No. 60-2585357 can be used.

Although silver halide emulsions may be used unripe, they are usually used after being chemically sensitized.0 Emulsions for conventional light-sensitive materials include well-known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526, JP-A-58-215644).
.

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

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

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

Organic compounds that can be used to form the above organic silver salt oxidizing agent include those described in U.S. Pat. No. 4,500,626 j11'
There are benzo)+77soles, fatty acids, and other compounds described in columns s52 to 53. Also, JP-A-Sho Go-1132
Silver salts of carboxylic acids having a furkynyl group, such as silver phenylpropiolate described in No. 35, and JP-A-Sho G! -249
Acetylene silver described in No. 044 is also useful. Two or more types of organic silver salts may be used in combination.

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

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) 24-25, the nitrogen-containing carvone wljilt and phosphoric acids described in JP-A-59-168442, or the mercapto compounds and mercapto compounds described in JP-A-59-1111336. Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in JP-A-61-147244, page (24).

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, holobo-2-cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, RD17029 (1978) 12-1
Sensitizing dyes described on page 3, etc., and JP-A-60-111239
No. 62-32445.

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, US Pat. No. 933,390, No. 3,635,72
No. 1, No. 3,743,510, No. 3,615,613
No. 3,615,641, No. 3. (317,295
No. 3,635,721).

The timing of adding these sensitizing dyes to the emulsion may be during or before chemical ripening, and US Pat.
It may be added before or after nucleation of silver halide grains according to No. 513 and No. 4,225,666, and the amount added is generally about 10''m to 10@-2 mol per mol of silver halide.

A hydrophilic binder is preferably used in the heat-developable photosensitive element of the present invention. The hydrophilic binder is preferably transparent or semi-transparent, and includes natural compounds such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, polysaccharides such as dextran, pullulan, etc., and polyvinyl alcohol. , polyvinylpyrrolidone, a partially saponified product of a copolymer of vinyl alcohol and acrylic acid, an acrylic heptagonal polymer, and other synthetic polymer compounds such as the water-soluble polyvinyl compound described in Japanese Patent No. 1111 Sho 62-245260, etc. include,
Two or more of these binders can also be used in combination. In addition to these, it is also possible to use dispersed vinyl compounds which are used in latex form and increase the dimensional stability of the photographic material.

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

In the present invention, hydrophobic additives such as reducible dye-donating compounds and electron donors can be incorporated into the layers of the photosensitive element by known methods such as those described in U.S. Pat. No. 2,322,027. . In this case, JP-A-59-83
No. 154, No. 59-178451, No. 59-1784
No. 52, No. 59-178453, No. 59-17845
No. 4, No. 59-178455, No. 59-178457
A high boiling point organic solvent such as those described in No. 1, etc. can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. *No more than 0.5c of ice per 1g of binder
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 made into fine particles and dispersed in the paint, in addition to the method described above.

When dispersing a hydrophobic compound in a hydrophilic colloid, various surfactants can be used.
-157636, pages (37) to (38), those listed as surfactants can be used.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. 4,500.
, No. 626, columns 51-52.

In a system that forms images by diffusion transfer of dyes, a dye fixing element is used together with the photosensitive material.1 Even if the dye fixing element is coated separately on a support separate from the photosensitive material, the dye fixing element is attached to the photosensitive material. The relationship between the light-sensitive material and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Pat. No. 4,500.626. The relationship described in column 57 is also applicable to the present application.

The dye-fixing element preferably used in the present invention has at least i/I waste containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in U.S. Pat. Mordant described in JP-A-60-118834, JP-A-60-118834
No. 119557, No. 60-235134, Patent Application No. 1983
Examples include those described in No. 87180, No. 61-87181, and the like. Also, U.S. Patent No. 4,463,0
A dye-receiving polymer compound as described in No. 79 M may also be used.

The dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective dust.

As the binder for the constituent layers of the dye fixing element, natural or synthetic polymeric substances similar to the binders of photosensitive materials can be used.

One or more layers of the 61 layering of photosensitive materials and dye-fixing elements include thermal solvents, plasticizers, anti-fading agents, UV absorbers, slip agents, matting agents, antioxidants, increasing dimensional stability. A fractional vinyl compound, a surfactant, a fluorescent whitening agent, etc. may also be included.

Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32). Also, dye fixation'g! is particularly important in systems where thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water. - It is preferable to include a base and/or a base precursor as described below in the base in order to improve the storage stability of the light-sensitive material. Image formation accelerators that can be used include those that promote redox reactions between silver salt oxidizing agents and reducing agents, promote reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitizers. It has functions such as promoting the movement of dye from the material layer to the dye fixed layer, and from a physicochemical function, it is a base or base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, and a surfactant. It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,878.
, 739, No. 38-409.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. Also, there are combinations of compounds that can react to form a complex with the metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), and compounds that generate bases by electrolysis as described in JP-A No. 61-232451. Can be used as a base precursor.

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 element separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing element 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 i-electron compounds, nitrogen-containing heterocyclic compounds, norcapto compounds and their precursors that undergo a substitution reaction with a coexisting base when heated (for example, U.S. Pat. No. 4.67
No. 0.373, No. 4,65 (No. 3,126, No. 4,61)
No. 0,957 or No. 4゜626.499, No. 4,6
No. 78,735, 4゜ (No. 339,408, JP-A-Sho (
No. 31-147249, No. G1-147244, No. 6
No. 1-184539, No. G1-185743, No. 61
-185744, 61-188540, 61-
No. 269148, compounds described in No. 61-2139143, etc.).

Preferably, the dye-fixing element is stored at a relative humidity of 25-85%.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive material layer V of the present invention or the dye fixing element may contain an inorganic or organic hardening agent.

Specific examples of hardeners include U.S. Pat. No. 4,678.739 Pt
rJ411fM, JP-A-59-11F36551: These can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing element of the present invention is one that can be heated to processing temperatures.

- As numerical supports, glass, paper, polymer films, metals and their analogues are used, as well as those described as supports in JP-A No. 51-147244, page (25). can be used.

The photosensitive material and/or the dye fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements. As a resistance heating element, 1! is an inorganic material that exhibits semiconductivity. There are two methods: one that uses a film, and one that uses an organic thin film in which conductive particles are dispersed in a binder. Materials that can be used in these methods include those described in JP-A-61-145544 and the like. Note that these conductive layers also function as an antistatic layer.

In the present invention, the method described in US Pat. No. 4,500,626, Nos. 55 to 56a can be applied to the coating method of the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers. .

As a light source for image exposure for recording an image on a photosensitive material, radiation including visible light can be used. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as seed lamps, xenon lamps, laser light sources, CRT light sources, light emitting diode (LED), etc., are used in US Pat.
The light source described in No. 56IIA of No. 00626 can be used.

The heating temperature in the heat development process can be developed at about 50°C to about 250°C, but it is particularly useful to use a heating temperature of about 0°C to about 180°C.The dye diffusion transfer process is carried out at the same time as the heat development. or after the heat development process is completed; in the latter case,
The heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 50° C. or higher and up to 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
56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used for the transfer of the diffusible dye to the dye fixed layer include water or a basic aqueous solution containing an alkali metal salt or an organic base [(
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 water W liquid can also be used. Further, a surfactant, an anti-capri agent, 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 a dye fixing element, a light-sensitive material, or both.

The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). It is also possible to use the solvent by preliminarily incorporating it into the photosensitive material, the dye fixing element, or both, 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 element. Hydrophilic thermal solvents are used for photosensitive materials and dye fixation I! : It can be built into either of the cables (
Although the layer to be incorporated may be any of the emulsion layer, the transparent layer, the dye fixing layer, and the dye fixing layer, it is preferable to incorporate it in the dye fixing layer and/or the layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, pyrinones, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

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

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a method described in No. 7244, pages (26) and (27).

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye fixing element and bringing them into close contact are described in VF 1986-147.
The method described in No. 244, page 27 can be applied.

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

The light-sensitive material of the present invention provides a blurred color image on a dye-fixing element through a thermal development-transfer process. In the photosensitive material from which the dye-fixing element has been removed after processing (if coated), a dark color image based on the unreacted dye-providing compound remains along with the silver halide and developed silver. Therefore, the photosensitive material of the present invention can be printed onto ordinary color paper or the like using this negative color image. Specifically, after heat development and transfer processing, the photosensitive material is desilvered using a known bleach-fix solution or a bleach and fix solution, followed by post-processing such as washing with water, and dried. Color images can be obtained. That is, the photosensitive material of the present invention not only provides a positive image through thermal development and transfer processing, but also can be used as a negative photosensitive material for reprints.

Here we will describe how to prepare the emulsion (1) for the seventh layer.

A well-stirred gelatin aqueous solution (containing 209 gelatin and 32 sodium chloride in water/000d, 7j'CK
K) Aqueous solution containing sodium chloride and potassium bromide &00yttl and silver nitrate aqueous solution (water t0
Silver nitrate 0.0xtl. J-2 moles dissolved) were simultaneously added at equal flow rates over 4 LO minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine ro molar) with an average grain size of 0°3Jμ was prepared.

Sodium thiosulfate after washing with water and desalting! ηtobi-hydroxy-6-mether/, J, Ja, 7-chitrazaindene 2
011J9 was added to perform chemical sensitization from to 0c. The yield of the emulsion was tooy.

Next, the method of preparing the emulsion (n) for the third layer will be described.

A well-stirred gelatin solution (water ioo.

3 ml of gelatin and sodium chloride? including 7
An aqueous solution too- containing sodium chloride and potassium bromide (kept at 30 C), an aqueous silver nitrate solution (0.22 mol of silver nitrate dissolved in 00 txl of water), and the following dye solution (I) were added. , simultaneously added at equal flow rates over μθ minutes. In this way, the average particle size is 0. ,
! A monodispersed cubic silver chlorobromide emulsion with jμ dye adsorbed (
bromine (10 mol%) was prepared.

Sodium thiosulfate after washing with water and desalting! ■ and goohydroxy-6-methyl-/, J, Ja, 7-chitrazaindene 2
Chemical sensitization was carried out at to''c by adding 0'lq. The yield of the emulsion was tooy.

Dye solution (I) Dye with the following structure: ito misaki methanol ≠00td Next, the method of preparing the emulsion (In) for the first layer will be described.

A well-stirred gelatin aqueous solution (dissolve gelatin, 202 and ammonium in 1000 atm of water, tooC
An aqueous solution containing potassium iodide and potassium bromide (kept at a temperature of
00.1 with 1 mole of silver nitrate dissolved in p
It was added while keeping the Ag constant. In this way, a monodisperse octahedral silver iodobromide emulsion (5 mol % of iodine) with an average grain size of 0.2 μm was prepared.

After washing with water and desalting, chloroauric acid (dahydrous salt)! Gold and sulfur sensitization was performed to oc by adding 1 and 2η of sodium thiosulfate. The yield of the emulsion was /cape.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Weigh out yellow dye-donating substance (1) in ivy, 22 in electron donor (ED-G), and 22 in tricyclohexyl 7 phosphate, add aml of cyclohexanone, and dissolve by heating to about to''c to form a homogeneous solution. This solution and a 10% solution of lime-treated gelatin 1009.Water 4QCC
and sodium dodecylbenzenesulfonate/,!
After stirring and mixing 9 and 1, mix with a homogenizer for 70 minutes.
Dispersed at 1000 orp. This dispersion is called a yellow dye-providing substance dispersion.

Similar to the dispersion of yellow dye-providing substance, the dispersion of magenta and cyan dye-providing substances is either magenta dye-providing substance (2) or cyan dye-providing substance (2).
It was made using

In Photosensitive Material 10/, except that 20% of the amount of electron donor (ED-J) added in each of the first layer, third layer, and first layer was replaced with the compound of the present invention shown below, Material′
Photosensitive material toko~10 having the same configuration as pr10/
I created j.

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

A dye fixing material R-/ was prepared by applying the following composition onto a paper support laminated with polyethylene.

Composition of dye fixing material R-/ Silicone oil tank 1 (CH2) 3 COOH Surfactant bone 2 Aerosol OT 3H7 Surfactant bone 4 Polymer old 5 Vinyl alcohol sodium acrylate copolymer (7!
72! molar ratio) Polymer tank 7 Demeron strand (70,000 molecule ft) mordant tank 6 SO□ and high boiling point organic solvent tank 8 Reofuosta! (Ajinomoto ■Crack) Matting agent Tatami 10 Benzoguanamine resin Percentage of particles exceeding 10 μm B, G, R, and gray color separation filters using a tungsten light bulb in the above multilayered color photosensitive material and continuously changing density vI for 1 second at 200 lux through
, I paid it back.

Water of /jzl/m2 was supplied to the emulsion surface of this exposed light-sensitive material using a wire parer, and then the material was superimposed so that the dye-fixing material and the film surface were in contact with each other.

The film was heated for 13 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was rr 0c or t'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 1 shows the results of measuring the maximum density (Dmax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.

The photosensitive material containing the compound of the present invention has a low Dmin;
It was also found that stable images can be obtained even when the developing temperature fluctuates.

Example 2 Photosensitive material of Example 1 10/~lO! and dye fixing material R-
7 and the development conditions were tj 0c/j seconds and ♂60c.
It was processed in two ways for 2j seconds. Other operating methods are the same as in Example. Photosensitive materials IO2 to 1O containing the compound of the present invention! It was found that stable images can be obtained even when the redemption time fluctuates.

Example 3 Using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as in color photosensitive material 10/ of Example 1, a multilayer color photosensitive material 30/ having the structure shown in Table 3 was prepared. Note that unless otherwise specified, the same additives as in Photosensitive Material 101 were used.

The organic silver salt emulsion was prepared as follows.

Ceratin 20f Tobi-acetylaminophenylpropiolic acid! ,the law of nature? 091% sodium hydroxide aqueous solution 10
It was dissolved in 00td and ethanol-〇〇-. The solution was kept at ao 0c and stirred. Silver nitrate μ in this solution! 2
A solution of 0.00ml of water was added over 5 minutes. Excess salt was then removed by sedimentation. Then the pH was adjusted to 6.3.
Accordingly, an organic silver salt dispersion with a yield of 3,009 ml was obtained.

Further, antifoggant precursor (1)'' having the following structure was added in 0.0 times the mole to the dye-donating substance, and dispersed in oil according to the method of Example 1 together with the dye-donating substance and the electron donor.

Similarly to Example/, 11% of the amount of electron donor (ED-4) added in each layer of the 7th layer, 3rd layer, and 3rd layer was added to the compounds (1), (5), and (7) of the present invention. , (11), (12), (21
) and (2) were replaced to create photosensitive materials l/+302 to 301.

Next, the method of preparing the dye fixing material (R-2) will be described.

Poly(methyl acrylate-N,N,N-)rifthyl-N-vinylbenzylammonium chloride) (The ratio of methyl acrylate and vinylbenzylammonium chloride is /:/) 10? was dissolved in 20117ml of water and mixed homogeneously with 1ooy of 70% lime processed gelatin.

A film-breaking agent was added to this mixed solution, and the mixture was uniformly applied to a wet film thickness of 0.8 m on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material (R-2) having a mordant layer.

After exposure as in Example/lro”c and izr’
The mixture was heated uniformly for 20 seconds on a heat block heated to c.

After supplying 20 td/FFI of water to the film surface side of the dye fixing material (R-2), the heat-treated photosensitive materials were stacked on the fixing material so that their film surfaces were in contact with each other.

Thereafter, the line speed was set to 2 mm in a laminator heated to
/aeC and then peeling off both materials to obtain a positive image on the dye-fixing material.

Dma for some cyan, magenta, and yellow colors
xI! :Dmin was measured. In the photosensitive materials 302 to 301 to which the compound of the present invention was added, stable images were obtained against fluctuations in development temperature.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Document February 1, 1927, Case Indication: Showa T-Co Patent Application No. 30 Hirotata No. 2, Title of Invention: Heat-developable Color Photosensitive Material 3, Amendment Relationship with cases involving patent applicants Contact information for patent applicants 〒10
6 4, 2-26-30 Nishi-Azabu, Minato-ku, Tokyo, Subject of the amendment The description in the "Detailed Description of the Invention" section 5 of the description and the "Detailed Description of the Invention" section of the description of the contents of the amendment is as follows. Correct as shown.

1) On page 6F/j to line 17, compounds represented by the following formulas CI and/or Cl are particularly preferred as electron donors (or precursors thereof). ” to be deleted.

2) Page 26, line 1r r(X-/) or [X-2]" r(X-1) or (X-II)J and correct it.

3) 1st/page/, lines 2-13 r(X-13, compound represented by (X-1f)") ETAJ and correct it.

4) First! Delete from line 72 of page to line 1r of page 26.

5) 3rd line from the bottom of page 1/J "r(ED-7)" r (ED-A) /J, 4fj and correct it.

Claims (1)

[Scope of Claims] A heat-developable color having on a support at least a photosensitive silver halide emulsion, a binder, a reducing agent or its precursor, and a reducible dye-providing compound that releases a diffusible dye when reduced. In the photosensitive material, the following general formula [I]
A heat-developable color photosensitive material comprising a compound represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, RED means redox nucleus, and if it is possible to release -(TIME)_n-FA by being oxidized during the development process. It is an atomic group that binds. TIME represents a timing group linked to RED with S, N, O or Se, and n represents an integer of 0 or 1. FA represents a group which functions as a fogging agent or a development accelerator for silver halide after being released from -(TIME)_n-FA.