JPH0264634A - Thermodevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the picture density and the color reproducibility of the subject material by interposing a substantially nonphotosensitive intermediate layer contg. a specified compd. between two kinds of photosensitive layers having different color sensitivities with each other. CONSTITUTION:The nonphotosensitive intermediate layer contg. the compd. shown by formula I is interposed between the two kinds of the photosensitive layers having the different color sensitivities with each other. When three kinds of the photosensitive layers having different color sensitivities with each other are used for the photosensitive material, the intermediate layers are preferably interposed among each of the photosensitive layers respectively. When the intermediate layer is constituted of plural layers, the compd. shown by formula (I) contd. in each of the intermediate layers may be the same compd. or the different compds. with each other. In formula I, X is a group capable of functioning as a development restrainer after being released from a group (Time)t-X. Thus, the picture accuracy and the color reproducibility of the photosensitive material are improved.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a heat-developable color photosensitive material, and in particular a heat-developable color photosensitive material that has good color reproducibility and can obtain high-density positive images. It's about materials.

(Background Art) 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 & I (published by Corona Publishing Co., Ltd. in 1982), pages 242 to 255. Page, US Pat. No. 4,500,626, etc.

For example, U.S. Pat.
An oxidized compound that does not have dye-releasing ability is made to coexist with a reducing agent or its precursor, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the remaining unoxidized reducing agent is A method of reducing and releasing a diffusible dye has been proposed. Also, European Patent Publication No. 22074
No. 6, Publication Techniques 87-6199 (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.

(Problem to be Solved by the Invention) However, 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 that staining of color images is high. It turns out that there is.

In order to suppress staining in a photothermographic material for positive image formation 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. However, the generated electron transfer agent radicals diffuse into other layers with different color sensitivities, cross-oxidize the electron donors there, and further promote Capri development, resulting in a decrease in image density. There was a problem in that color reproduction deteriorated due to this.

In order to solve these problems, attempts have been made to provide an intermediate layer between photosensitive layers with different color sensitivities or to contain a reducing substance in this intermediate layer, but For photosensitive materials, image forming speed, resolution,
From the viewpoint of film quality, etc., there are restrictions on the amount of binder in the intermediate layer and the amount of reducing substance added, so a sufficient improvement effect could not be obtained.

In addition, the problem that image density decreases due to the progress of fogging development remains.

An object of the present invention is to increase image density and improve color reproducibility in a heat-developable color photosensitive material.

(Means for Solving the Problems) An object of the present invention is to provide a support with at least a photosensitive silver halide emulsion, a binder, an electron donor, an electron transfer agent, and a coating that releases a diffusible dye when reduced. In a heat-developable color photosensitive material having a reducible dye-providing compound, the following general formula (I
) This was achieved by a heat-developable color photosensitive material characterized by having a substantially non-photosensitive intermediate layer containing the compound represented by:

General Formula (I) % Formula % In the formula, A means a redox mother nucleus, and is an atomic group that makes it possible to release +TimefLX by being oxidized during development processing.

Time represents a tanning group connected to A using SXN, O or Se, and t represents an integer of 0 or 1.

X represents a group that functions as a development inhibitor after being released from +Time+uX.

Hereinafter, the compound having the general formula (R) used in the present invention will be explained.

First, A in general formula (+) will be explained in more detail. A
Examples of the redox nucleus represented by include hydroquinone, catechol, p-aminophenol, 0-aminophenol, 1,2-naphthalenediol, 1,4-naphthalenediol, 1゜6-naphthalenediol, 1,2
-aminonaphthol, 1,4-aminonaphthol or 1
, 6-aminonaphthol, etc. At this time, the amino group is a sulfonyl group having 1 to 25 carbon atoms, or a sulfonyl group having 1 to 25 carbon atoms.
Preferably, it is substituted with ~25 acyl groups. 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 amino group that forms the redox nucleus may be protected with a protecting group that can be removed during development. Examples of protecting groups include those with 1 to 25 carbon atoms, such as acyl. group, an alkoxycarbonyl group, a carbamoyl group, and the protecting groups described in JP-A-59-197037 and JP-A-59-201057. Furthermore, this protecting group
If possible, it may be combined with the substituents of A described below to form a 5, 6- or 7-membered ring.

The redox nucleus represented by A may be substituted with an appropriate substituent 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 +'l '
Examples include ime+zX. These substituents may be further substituted with the substituents mentioned above, and if possible, these substituents may be bonded to each other to increase the number of saturated or unsaturated carbon atoms, or the number of saturated or unsaturated carbon atoms. A heterocycle may also be formed.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, 1,
Examples include 4-naphthalenediol and 1,4-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 (I) are shown below. In each structural formula, (*) represents ÷Time+, and indicates the bonding position of X.

0■ 0H 0■ Cotel+3 Among these, a redox core having a group imparting diffusion resistance is preferred.

+Time-)-1X is a group that is released as e+Time-, X only when the redox mother nucleus represented by A in the general formula (+) undergoes a cross-oxidation reaction during development and becomes an oxidized product.

Time is a timing group that connects to A with a sulfur atom, nitrogen atom, oxygen atom, or selenium atom, and e-(-Time-)-, which is released during development, undergoes one or more reaction steps from Examples include groups that release X. As Time, for example, U.S. Patent No. 4,248
, No. 962, No. 4.409.323, British Patent No. 2
, 096,783, U.S. Patent No. 4,146,396, Publication No. 146828/1982, Publication No. 57-568
Examples include those listed in No. 37.

Time may be a combination of two or more selected from those listed above.

X means a development inhibitor. Examples of development inhibitors include:
Examples include compounds having mercapto a bonded to a heterocyclic ring or heterocyclic compounds capable of producing iminosilver. Examples of compounds having a mercapto group bonded to a heterocycle include substituted or unsubstituted mercaptoazoles (e.g., 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole, 1-butyl-5- Mercaptotetrazole, 2-methylthio-
5-Mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercap)-1,2,4-triazole, 1-(4-ethylcarbamoylphenyl)
-2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2
-Mercapto-5-sulfobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-5-sulfobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto1.3.4-oxadiazole, 1-(3-(3-methylureido)phenyl)-5-mercaptotetrazole, 1-(4-
Nitrophenyl)-5-mercabutotetrazole, 5-
(2-ethylhexanoylamino)-2-mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (e.g., 6-methyl-4-mercapto-1,3,3a, 7-titrazaindene, 46-simethyl- 2-mercapto-1,3,3a7-chitrazaindene, etc.), i! Substituted or unsubstituted mercaptopyrimidines (e.g. 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, etc.)
and so on.

Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted triazoles (for example, 1 2
4-) Riazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-bromobenzotriazole, 5-n-butylbenzotriazole, 56-dimethylbenzotriazole, etc.), substituted or unsubstituted indazoles (such as intasole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5 - ditroindazole, etc.),
Examples include substituted or unsubstituted benzimida (eg, 5-nitrobenzimidazole, 5,6-cyclobenzimidazole, etc.).

Further, after X separates from Time in the general formula (I) and once becomes a compound having development inhibiting properties, it further causes a certain chemical reaction with the developer components to substantially have development inhibiting properties. Functional groups that undergo such chemical reactions, which may not be present or may be changed into compounds with significantly reduced amounts, include, for example, ester groups, carbonyl groups,
Examples include an imino group, an ammonium group, a Michael addition acceptor group, and an imide group. Examples of such deactivated development inhibitors include 1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1
-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(3-maleinimidophenyl)-5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5-(4-dianophenoxycarbonyl)benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3゜4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5-(2,3-dichloropropyloxycarbonyl)benzotriacy/L/, 1-( 4-benzoyloxyphenyl)-5-mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1-(3-vinylcarbonylphenyl)-5-mercapto Tetrazole, 5-succinimidomethylbenzotriazole, 2-(4-succinimidophenyl)-5-mercapto-1,3,4
-oxadiazole, 6-phenoxycarbonyl-2-
Examples include mercabutobenzoquinazole.

In order to more specifically list the contents of the present invention, the compound represented by the general formula (I) (D I R compound IFI) will be described below.
Specific examples are shown below, but the compounds that can be used in the present invention are not limited to these.

Compound 1 Compound 2 H H Compound 4 Compound 5 H Compound 7 Compound 8 Kano H Compound? 1ff3 Compound 6 Compound 9 Compound 43 Compound 46 0 ■ Compound 48 Compound 51 Compound 53 0 ■ NO7 Compound 44 Compound 45 Compound 50 1I Compound 52 H Compound 54 Compound 58 Compound 61 Compound 63 H Compound 65 Compound 67 Compound 59 Compound 62 Compound 64 Compound 66 Compound 68 Compound 60 H The compounds shown in General 2N) are known compounds, -
It can be synthesized by the following two methods.

First, if Time is a simple bond (t −0), the first
is benzoquinone, orthoquinone, or quinone in chloroform, 1,2-dichloroethane, carbon tetrachloride, or tetrahydrofuran without a catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, or methanesulfonic acid. This method involves reacting a monoimine, a quinone diimine derivative, and a development inhibitor at a temperature between room temperature and 100°C. The second is acetone,
Benzoquinone, orthoquinone, quinone monoimine, and quinone diimine derivatives substituted with chlorine, bromine, or iodine in the presence of a base such as potassium carbonate, sodium bicarbonate, sodium hydride, or triethylamine in an aprotic polar solvent such as tetrahydrofuran or dimethylformamide. In this method, a quinone compound obtained by reacting a development inhibitor with a developer at a temperature between -20°C and 100°C is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfide. [Reference: Re5earchDi
sclosure 18227 (I979);
LiebigsAnn, Chem, 764.131 (
I972)) Next, the type (t, -1) in which X is released via Time can be synthesized in substantially the same manner as above. That is, instead of the above development inhibitor (X), T
A method of using ime-X or first introducing Time having a substitutable group (for example, a halogen atom, a hydroxy group, or a precursor thereof) into the redox core, and then linking X by a substitution reaction. It is.

The amount of the compound of general formula (I) of the present invention added is 0.01 mmol to 1 rTf of the support in each intermediate layer.
10 mmol, preferably 0.1 mmol to 5 mmol, in each interlayer, 0 per gram of binder in that layer.
．． 0.1 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol.

In the present invention, the general formula (
A substantially non-photosensitive intermediate layer containing a compound of I) is provided.

When there are three sets of photosensitive layers each having a different color sensitivity, this intermediate layer is preferably provided between each photosensitive layer.

When there is a plurality of intermediate layers, the compounds of the general formula cN of the present invention added to each intermediate layer may be the same or different.

In the present invention, a reducible dye-donating compound is combined with an electron transfer agent and an electron donor, a binder, and a silver halide emulsion to form one unit of a photosensitive layer. 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.

In this case, the electron transfer agent and electron donor can be added to either the silver halide emulsion layer or the reducible dye-donating compound layer, but at least the electron transfer agent is present in the silver halide emulsion layer. preferable.

In the present invention, at least two sets of such photosensitive layers are used.

Normally, in order to reproduce full color, three sets of photosensitive layers having mutually different color sensitivities are provided. For example, there are three combinations of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a three-set combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can have various arrangements known in conventional color photonic materials.

Moreover, each of these color-sensitive layers may be divided into two or more layers as necessary.

As an example of a preferable layer structure of the heat-developable color light-sensitive material of the present invention, a support - a heat-developable red light-sensitive layer - an intermediate layer containing the compound of the present invention - a heat-developable green light-sensitive layer - an intermediate layer containing the compound of the present invention Layers - Heat-developable blue-sensitive layer - Protective layer, transparent support - Heat-developable blue-sensitive layer - Intermediate layer containing the compound of the present invention - Heat-developable green-sensitive layer - Intermediate layer containing the compound of the present invention - Heat development red-sensitive layer - protective layer, support - cyan dye-providing compound layer - red-sensitive emulsion layer - intermediate layer containing the compound of the present invention - magenta dye-providing compound layer - green-sensitive emulsion layer - containing the compound of the present invention It includes an intermediate layer, a yellow dye-providing compound layer, a blue-sensitive emulsion layer, a protective layer, and the like.

In addition to the above, the heat-developable color photosensitive material can be provided with various auxiliary layers such as an undercoat layer, a yellow filter layer, an antihalation layer, and a back layer.

The intermediate layer of the present invention may also serve as a yellow filter layer.

In the present invention, a reducing agent may be used in combination with the compound of general formula (I) in the intermediate layer. The reducing agent used in combination is
1i, those described in No. 62-279842 are preferably used. In particular, hydroquinones having a diffusion-resistant group as a substituent are preferably used. The amount used is in the range of 0.05 mmol to 10 mmol per M of support and 0.01 mmol to 10 mmol per gram of binder in each intermediate layer.

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

The reducible dye-providing compound used in the present invention is preferably a compound represented by the following general formula (C-1).

PWR-(Time)t-Dye General formula (C-1) In the formula, PWR is reduced to -(Time)
t [) represents a group that releases ye.

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

t represents an integer of 0 or l.

Dye represents a dye or its precursor.

First, PWR will be explained in detail.

PWR is U.S. Pat. No. 4,139,389, or U.S. Pat. No. 4,139,379, U.S. Pat.
Electron-accepting center and intramolecular nucleophilic substitution reaction in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-59-185333 and JP-A-57-84453 It may correspond to the part including the center, or it may correspond to the part including the center, or as described in US Pat. As disclosed, it corresponds to a part containing an electron-accepting quinonoid center and a carbon atom linking it to the photographic reagent in a compound that releases the photographic reagent by an electron transfer reaction in the molecule after being reduced. It's okay. Also, JP-A-56-14253
No. 0, U.S. Patent No. 4,343,893, U.S. Patent No. 4,619,
No. 884, the single bond is cleaved to release the photographic reagent after reduction, and the atom (
It may correspond to a moiety containing a sulfur atom, a carbon atom, or a nitrogen atom). Also, U.S. Patent No. 4,450
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group, as disclosed in No. 223, It corresponds to the geminal dinitro moiety in the dinitro compound that beta-desorbs the photographic reagent after electron acceptance and the moiety containing the carbon atom that connects it to the photographic reagent described in U.S. Pat. No. 4,609,610. It's okay.

In addition, a compound having SCh -X <x represents oxygen, sulfur, or nitrogen) and an electron-withdrawing group in one molecule as described in Japanese Patent Application No. 106885/1982;
106895, a po-x bond (X
is the same as above) and an electron-withdrawing group, c-x' in one molecule described in Japanese Patent Application No. 106887/1983
Examples include compounds having a bond (X' is synonymous with X or represents -SO3-) and an electron-withdrawing group.

In order to more fully achieve the object of the present invention, the general formula CC
Among the compounds of -1), those represented by the general formula (C1l) are preferred.

General formula (Cn) EAG'(Time-)-tD)'fll is RIOI, RI
O! Alternatively, it binds to at least one EAG.

The part corresponding to PWR of formula-10 (CI[) will be explained.

X represents a group (-N (R103) -) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

RIDI, Root oc and RI03 represent a group other than a hydrogen atom or a simple bond.

Groups other than hydrogen atoms represented by R1o', R"", and R"3 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, etc. These may have substituents.

RIOI and R163 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, and the like. R10
' and R10ff preferably have 1 to 40 carbon atoms.

R11e! Preferable examples of 0 are substituted or unsubstituted acyl groups and sulfonyl groups, which are the same as Root and the acyl groups and sulfonyl groups mentioned in the case of Root. The number of carbon atoms is preferably 1 to 40.

RIOI, RIDI and R103 may be bonded to each other to form a five- or six-membered ring.

As X, enzymes are particularly preferred.

EAG will be described later.

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

General formula (C■) EAG ・(Time÷, Dye is bonded to at least one of R+oa and EAG.

X has the same meaning as above.

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

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

General formula (A) In general formula (A), Zl represents -C-3ub or -N-.

(2) 7 represents an atomic group forming a two- to six-membered aromatic group together with Zl and zz, and n represents an integer from 3 to 3.

Vx 1-Zi-1Vai z3 Za-1V.

1-Zs -Z4-25-1Vb; -Zs -Z
aZ, Z, b-1Vti Z3 Z4 Z
s ZaZ, -1VsiZs Za Zs
ZbZv Za-.

Sub 5ub Zz Zs each represents 10--N--Oub-S-1 or 15O8-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Sub may be the same or different, or may be bonded to each other to form a king to six-membered saturated or unsaturated carbocycle or heterocycle.

In general formula (A), the sum of the eyelet substituent constant sigma para of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0°85 or more.

EAG is preferably a ring group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire chemical compound. Examples of 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 control the properties and reactive groups towards electrophilic groups.

A specific example of F and AC is European Patent Publication No. 220746A2
No. 6-7.

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

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244.
No. 36549 (8) pages - 00, patent application 1988-8862
Examples include the groups described in No. 5, pages (36) to (44).

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

Specifically, BP76.492A, JP 59-165
Dye disclosed in No. 054 can be used.

The compound represented by the above general formula (C1l) or (CII[) must itself be immobile in the photographic layer, so that E A Q , Rlot , R10!
8 carbon atoms at RI04 or X position (especially RAG position)
It is desirable to have the above ballast group.

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 can also be used.

C0NHC+ &H33(n) Cth H2'r SUR t13 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 is 0.05 to 5 mmol/n, depending on the extinction coefficient of the dye. , preferably 0.1~
It is in the range of 3 mmol/d. The dye-donating substances can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 251, mobile dyes having different hues are mixed, for example, cyan, magenta, and yellow dye-providing substances are mixed in a layer containing at least 1 m of silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of emitting dye-providing substances.

In the present invention, an electron donor and an electron transfer agent (ETA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Publication No. 87-6199, and the like. Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula (C) or (D).

General formula (C) OA. 1 OAAl General formula CD) OA,. 1 In the formula, A1°1 and A1°8 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, the nucleophilic reagent is OHO, Ro.

(R: alkyl group, aryl group, etc.), hydroxamic acid anion 1303 g (Anionic reagent such as El, unshared electron pair such as l or secondary amines, hydrazine, hydroxylamines, alcohols, thiols, etc.) Compounds with

A. Preferred examples of I, Alox are hydrogen atoms,
Acyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoboryl group, diarylphosphoryl group, or JP-A-59-197037, JP-A-59-2
It may be a protecting group disclosed in No. 0105, or A
lel s AlOR is R101, R1 if possible
0! , R103 and Rt@4 may be combined with each other to form a ring, and A1.l and Aloz may be the same or different.

R2.l, R20g, R163 and R104 are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, an imido group, Represents a carboxyl group, a sulfonamide group, etc. These groups may have an iYl group if possible.

However, the total carbon number of R21 to R104 is 8 or more. Furthermore, in the general formula (C), R201 and R"# and/or R"" and R"' are combined with each other to form a saturated or unsaturated ring. You may.

Among the electron donors represented by the general formula (C) or (D), those in which at least two of R201 to R*64 are substituents other than hydrogen atoms are preferred. Particularly preferred compounds are those in which at least one of R201 and R101 and at least one of R2O3 and R204 are 'yl 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.

Specific examples of the electron donor will be listed, but the invention is not limited to these compounds.

(ED-1) H (ED-2) H H (ED-3) H 0 ■ (ED-4) H 0 ■ (ED-5) H Ha H (ED-6) (ED-10) H H (ED-7) H (ED-8) H (ED-9) H R HlC H 83C-C-CHs C.I.

Any compound that exists in H3H (ED) can be used, but a mobile one is preferable.

A particularly preferable ETA is the following general formula (X-1) or (
This is a compound represented by X-11).

The amount of H electron donor (or its precursor) to be used has a wide range, but is preferably 0.0 per mole of positive dye donor.
A preferred range is from 1 mol to 50 mol, particularly from 0.1 mol to 5 mol. Also, 0 per mole of silver halogenide
．． 001 mol to 5 mol, preferably 0.01 mol to 1.0 mol.
It is 5 moles.

The ETA used in combination with these electron donors is oxidized by silver halide, and the ability of the oxidized form to cross-oxidize the electron donor is expressed as p3oh/\R30s (X-13 (×-■) in the formula , R represents an aryl group. R3G+ , R302R
303, R304, R30% and R3+6 are hydrogen atoms,
It represents a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and may be substituted if possible. Furthermore, these may be the same or different.

In the present invention, compounds represented by the general formula [X-■] are particularly preferred;
I, R3OR, R303 and R304 are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group, more preferably a hydrogen atom or a methyl group. , a hydroxymethyl group, a phenyl group, or a phenyl group substituted with a hydrophilic group such as a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group.

Specific examples of ETA are shown below.

(X-1) (X-2) (X-5) (X-7) (X-6) (X-8) (X-9) (X (X-3>(X-4> (X- 11> (X-13) (X-12) (X-14) The ETA precursor used in the present invention does not have a developing effect during the storage of the anti-glare material before use, but it has a suitable activator. (For example, a base, a nucleophile, etc.) or a compound that can only release ETA by the action of heating.

In particular, the ETA precursor used in the present invention has a reactive functional group blocked with a blocking group.
Although it does not function as an ETA before development, it can function as an [iAT] because the blocking group is cleaved under alkaline conditions or when heated.

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

The ETA@ precursor used in the present invention is a known compound, for example, US Pat. No. 767.704, US Pat. No. 3,241
．． No. 967, same No. 3. 246. No. 988, No. 3,
No. 295,978, No. 3.462.266, No. 3
, No. 586,506, No. 3,615.439, No. 3,650,749, No. 4.209.580, No. 4,330.617, No. 4,310,612 ,
British Patent No. 1.023,701, British Patent No. 1.23183
No. 0, No. 1,258.924, No. 1゜346.9
No. 20, JP-A-57-40245, JP-A No. 58-1139
The developer precursors described in No. 58-1140, No. 59-178458, No. 59-182449, No. 59-182450, etc. can be used.

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

ETA and an ETA precursor can also be used in combination.

In the present invention, the combination of electron donor and ETA is preferably incorporated into the heat-developable color photosensitive material. Electron donors, ETAs, or their precursors can be used in combination of two or more, and can be used in emulsion layers (blue-sensitive layers, green-sensitive layers, red-sensitive layers, infrared-sensitive layers, ultraviolet-sensitive layers, etc.) in light-sensitive materials. It can be added to each emulsion layer or only to some emulsion layers.
Further, it can be added to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, protective layer, etc.), or even to all layers. The electron donor and ETA can be added to the same layer or to separate layers. Additionally, these reducing agents can be added in the same layer as the dye-donating substance or in a separate layer; however, it is preferable that the diffusion-resistant electron donor be present in the same layer as the dye-donating substance. preferable,
ETA can be incorporated into the image-receiving material (dye fixing layer), or if a small amount of water is present during thermal development, it can be dissolved in this water. The preferred amount of the electron donor, ETA, or their precursor used is 0.01 to 50 mol in total, preferably 0.01 to 50 mol, preferably 0.01 to 50 mol in total, per 1 mol of the dye-donating substance. 1
~5 mol, total amount 0.00 per mol of silver halide
The amount is 1 to 5 mol, preferably 0.01 to 1.5 mol.

Moreover, ETA is 60 mol% or less, preferably 40 mol% or less of the total reducing agent. When ETA is supplied dissolved in water, the concentration of ETA is 10-4 mol/! ~1 mol/
l is preferred.

In order to introduce the compound of general formula (I) of the present invention, a dye donating substance, an electron donor, an electron transfer agent or their precursors and other hydrophobic additives into the hydrophilic colloid layer, a high boiling point organic solvent is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) Acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide)
, fatty acid esters (e.g. dibutoxyethylsuccinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) Patent application 1986-23
Carboxylic acids described in No. 1500, JP-A-59-8315
No. 4, No. 59-178451, No. 59-178452
No. 59-178453, No. 51-178454, No. 59-178455, No. 59-178457 using the method described in U.S. Patent No. 2,322,027, or Boiling point: approx. 30°C ~ l 6
0 'C organic solvents such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
After dissolving in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point 4m t3 medium and a low boiling point organic solvent may be mixed and used.

Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like as required. 1ff with high boiling point
i? The amount of the 6 medium is 10 g or less, preferably 5 g or less per 1 g of the dye-donating substance used. Further, the amount is 5 g or less, preferably 2 g or less per 1 g of the diffusion-resistant reducing agent. Furthermore, 1 g of high boiling point organic solvent per 1 g of binder.
Below, preferably 0.5g or less, more preferably 0.5g or less.
3g or less is appropriate. Also, Special Publication No. 51-39853,
The dispersion method using a polymer described in JP-A-51-59943 can also be used. They can be directly dispersed in the emulsifier, or they can be dissolved in water or alcohols and then dispersed in gelatin or in 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-59-174830, JP-A No. 53-1
02733, Japanese Patent Application No. 62-106882, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used.
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound on a support, and if necessary, An organic metal salt oxidizing agent or the like can be contained therein. These components are often added to the same layer, but if they are in a reactable state, they can be added separately to separate layers.For example, a colored dye-providing compound may be added to the lower layer of the silver halide emulsion. If present in , a decrease in sensitivity can be prevented. The reducing agent is preferably 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 cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.

Examples include a 3N combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

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 back layer.

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 is a surface latent image type emulsion. A surface latent image type emulsion is an emulsion in which a latent image is mainly formed on the grain surface, and the definition of a zero surface latent image type emulsion, also called a negative type emulsion, is described in Japanese Patent Publication No. 58-9410.

The silver halide emulsion of the present invention may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The acceptable particle size is 0.1~
The crystal habit of the halogenated root grains, which is preferably 2μ, particularly preferably 0.2 to 1.5μ, may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or the like.

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

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

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 to 1 Og/r/ 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, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids, and other compounds described in column 53, etc. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044. 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°Ol to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 to 1 Og#d in terms of silver.
is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD17
643 (I978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and their Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used. In an embodiment of the present invention, it is preferable to add a mercapto compound to the photosensitive layer and add the compound of the present invention to the intermediate layer.

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

Specifically, U.S. Pat.
17029 (I978), pages 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing 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, patent application No. 61-22
6294 etc.).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, and may be added to the emulsion as described in US Pat. No. 4,183.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666. The amount added is generally about 10-'' to 104 moles per mole of silver halide.

A hydrophilic binder is preferably used as the constituent phase 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 natural compounds such as proteins such as gelatin, gelatin derivatives, or cellulose derivatives 1, starch, polysaccharides such as acacia, dextran, pullulan, and polyvinyl alcohol. , polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, super absorbent polymers described in JP-A-62-245260 etc., namely -COOM or -3O3M
(M is a hydrogen atom or an alkali metal) homopolymer of vinyl monomer or this vinyl heptamer-IJ
Alternatively, copolymers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. Two or more of these binders can also be used in combination.

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

In the present invention, the amount of binder applied is 20 per 1 d.
The amount is preferably 10 g or less, more preferably 7 g or less.

Constituent layers (including bank layers) of photosensitive materials or dye-fixing materials contain various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. can get.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent No. 4,50.
No. 0,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye fixing material is used together with a photosensitive material. It may also be coated on the same support. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of U.S. Pat. No. 4,500,626 can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

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

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 62 of JP-A-62-253159.
-245253, etc.

Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used. Examples include various modified silicone oils described in "Modified Silicone Oil" technical data P618B published by Shin-Etsu Silicone,
In particular, carboxy-modified silicone (product name X-22-3)
710) etc. are effective.

Also, Japanese Patent Application Publication No. 62-215953, Japanese Patent Application No. 622368
The silicone oil described in No. 7 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

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

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A No. 46-2784, etc.), and other JP-A Nos. 5148535 and 62-136.
There are compounds described in No. 641, 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
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1983-234103, JP-A No. 62-31096, Japanese Patent Application No. 1983 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
The anti-fading agent described on pages I25) to (I37) for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or it may be added to the dye-fixing material from the outside. It may also be supplied to a dye fixing 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. For example, K. Veenkataraman 114rTh
e Chemistry of 5ynthetic
Dyes J Volume V Chapter 8, JP-A-61-143752
Examples include compounds described in No.

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

It can be used in combination with optical brighteners and anti-fade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Examples include hardeners described in No. 1-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, and epoxy hardeners (Ctlz-Cll-CL-0-(CL) h-0-C
tlz-CH-C)It etc.)\/
\1 O Vinylsulfone hardener (N,N'-ethylene-bis(
(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Various surfactants can be used in 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 slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of active fluoro compounds include JP-B No. 57-9053 No. 8-17@, JP-A No. 61-Sho.
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. can be mentioned.

Agent 77) can be used in photosensitive materials and dye fixing materials. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described in No. 6 (page 29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. 0065.

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. It is classified into precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or negative ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
, No. 739, columns 38-40.

Examples of 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 a poorly soluble metal compound and a compound (referred to as a complex-forming compound) that can undergo a complex-forming reaction with the metal ion forming the poorly soluble metal compound described in European Patent Publication No. 210,660, Japanese Patent Publication No. 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 coexisting bases 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 a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. -For boat fishing, paper and synthetic polymers (films) can be used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (e.g. triacetylcellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, and synthetic paper made from synthetic resin pulp such as polyethylene and natural parob. Mixed paper, 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 supports described on page 1) can be used.

A hydrophilic binder, an alumina sol, a semiconductive metal oxide such as tin oxide, a carbon blank, or other antistatic agent may be applied to the surface of these supports.

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 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 are methods of outputting the image to an image display device such as a spray display or a plasma display, and exposing the light directly or through an optical system.

Light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. as mentioned above, such as U.S. Pat. No. 4.500.6.
The light source described in No. 26, column 56 can be used.

Image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), etc. ), lithium iodate, inorganic compounds such as BaBz04, urea derivatives, nitroaniline derivatives, such as 3-methyl-
Nitropyridine-N-oxide derivatives such as 4-nitropyridine-N-oxide (POM), JP-A-61-5
Compounds described in No. 3462 and No. 62-210432 are preferably used.

As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

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

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

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

The heating temperature in the heat development step can be developed at about 0°C to about 25°C, and particularly useful is about 0°C to about 180°C. The dye diffusion transfer process may be performed simultaneously with the heat development or after the heat development process is completed. In the latter case, the dye diffusion transfer process may be performed at a temperature ranging from the temperature in the heat development process to room temperature, depending on the heating temperature in the transfer process. Although it is possible, it is particularly preferable to use a temperature of 50° 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
56, etc., a method in which development and transfer are performed simultaneously or successively 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 the medium (used to accelerate development and/or transfer the diffusible dye to the dye fixed layer) include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (
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 (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). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

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. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

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

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

Heating methods in the development and/or transfer process include contact with a heated block or plate, heat roller, hot breather, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. or passing through a high-temperature atmosphere.

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

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 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. can be preferably used.

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

Example 1 A well-stirred gelatin aqueous solution (20 g of gelatin, 1 g of potassium bromide, and OH (CHiz
S (CHi)z Add 0.5g of OH and keep warm at 50℃), add the following (I) solution, (II) solution and (I[I)
The liquids were added simultaneously at equal flow rates over 30 minutes. In this way, a monodisperse silver bromide emulsion having an average grain size of 0.42 μm and adsorbing a dye was prepared.

After washing with water and desalting, add 20g of lime-treated ossein gelatin, adjust the pH to 6.4 and pAg to 8.2, and then hold the gelatin at 60°C.
Sodium thiosulfate 9■, chlorauric acid 0.01
% aqueous solution 6-14-hydroxy-6-methyl-1,3,
3a,? - 190 μl of tetrazaindene was added and chemical sensitization was carried out for 45 minutes. The yield of emulsion was 635 g.

Y 11LLLL A well-stirred aqueous solution (gelatin 2 in 730 water)
0■, potassium bromide 0.30g, sodium chloride 6g,
and 0.015g of the following chemical A and kept at 60.0℃), the following solutions (I) and (II) were added at the same time to 60.0℃.
Added at equal flow rates over minutes. (I) After finishing adding the liquid,
A methanol solution (I[) of the following sensitizing dye was added.

In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm 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 chemical used at this time was triethylthiourea 1
．． 6■ and 4-hydroxy-6-methyl-1,3,3a,
The aging time was 55 minutes using 100 μl of 7-tetozaindene. The yield of this emulsion was 635 g.

A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide and HO (cHt
)
) was added at the same time over 30 minutes. Thereafter, the following solutions (IU) and (IV) were simultaneously added over 20 minutes. After the addition was completed, 30 cc of a 1% aqueous potassium iodide solution was added, and then the following dye solution was added.

After washing with water and desalting, add 20 g of lime-treated ossein gelatin and adjust the pH to 6.2 and pAg 8.5, and then add sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a.
,? - Optimal chemical sensitization was carried out by adding tetrazaindene and chloroauric acid. In this way, 600 g of a monodisperse octahedral silver iodobromide emulsion with an average grain size of 0.45 μm was obtained.

Dye-donating compound C0NHC+ hHss (n) C0NHC+J*, 1(n) Cyclohexanone 40d was added to the above recipe for colored gelatin yellow, magenta, and cyan, and dissolved by heating at approximately 60°C to form a homogeneous solution. . This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, and 0.0 g of sodium dodecylbenzenesulfonate. After stirring and mixing 6 g and 50 g of water, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of a dye-providing compound.

C0NIC+&Hss(n) -N 〇- Monoelectron donor Oll High boiling point solvent Zinc hydroxide with average particle size of 0.2μ 12゜5g1
As a dispersant, carboxymethyl cellulose IB and 0.1 g of sodium polyacrylate were added to 10 (l) of a 4% gelatin aqueous solution.
In addition to d, the average particle size is 0. The mixture was ground for 30 minutes using a 75-inch glass bead.

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

Using the material thus prepared, heat-developable color photosensitive material 1 having a multilayer structure shown in Table 1 was produced.

Additives other than those mentioned above in Table 1 are shown below as hardener (I) 1° bis(vinyl sulfo).

Nylacetamide) Ethane water-soluble polymer (I+ Sumikagel L-5 Sumitomo Chemical ■High boiling point organic solvent (I) Tonocyclohexylphosphate water-soluble polymer (2) SO, surfactant f1) Aerosol OT antifoggant (I ) ■ Antifoggant (2) Antifoggant (3) Table 2 (Continued) Each layer was coated with the composition shown in Table 2 on a paper support laminated with polyethylene to prepare a dye fixing material.

Table-2 In addition, The additives used are shown below.

silicone oil Cll3-3i-0 -(-S i +Tr−÷Si ÷]-3i-Ctl 3 CH3 (CH2): +C00It CH3 Surfactant (I) Aerosol OT Surfactant (2) C,F , 5OzNc) to IzCOO C3B.

Surfactant (3) CH.

C+ 1H23CONHCH2CII2CH2N■Cl
l2COOe polymer vinyl alcohol sodium acrylate copolymer (75/25 molar ratio) dextran molecular weight 70,000) Mantle agent benzoguanamine resin average particle size 10 μm Dispersed in gelatin in the second and fourth layers of photosensitive material 1 by oil dispersion method Comparative photosensitive material 2 was prepared by adding each of the following reducing agents (I) at a concentration of 0.36 mmol/I.

Mordant SO□ and high boiling point organic solvent Rheophos 95 (manufactured by Ajinomoto ■) Hardener/ ＼ (C1lz) a (O-CII C8-CHI)
z Photosensitive material 1 except that the compound of the present invention dispersed in gelatin by the oil dispersion method shown in Table 3 was added to the second and fourth layers at a concentration of 0.36 mmol/d. Photosensitive material 3 with similar configuration
7 was created.

The color light-sensitive material having the multilayer structure was exposed using a spectrograph through a wedge whose density was continuously changing in the direction perpendicular to the wavelength.

15d/ni on the emulsion surface of this exposed color photosensitive material.
of water was supplied using a wire bar, and then the dye-fixing material and the membrane surface were overlapped so that they were in contact with each other.

The film was heated for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C.

Next, when the dye-fixing material was peeled off from the light-sensitive material, a blue, green, and red spectral durum was obtained on the dye-fixing material in accordance with the wavelength.

Table 3 shows the results of measuring the density of cyan and magenta in the blue light part, cyan and yellow in the green light part, and magenta and yellow in the red light part.

Table 3 shows that by adding the compound of the present invention to the intermediate layer, color reproduction is improved and images with high density can be obtained.

Similar results were obtained when the support for the heat-developable color photosensitive material was replaced with a paper support laminated on both sides with polyethylene.

In addition, reducing agent (I) added to the intermediate layer (second layer, fourth layer)
) Or, similar results were obtained even when the method of preparing a gelatin dispersion of the compound of the present invention was changed from an oil dispersion method to a polymer dispersion method or a fine particle dispersion method.

Details of the oil dispersion method, polymer dispersion method, and fine particle dispersion method are shown below.

Oil dispersion method 20 mmol of reducing agent (I) or the compound of the present invention is mixed with 2 g of triisononyl phosphate and 30 mmol of ethyl acetate.
d at about 60°C to make a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, and 60 g of water
and 1.5 g of sodium dodecylbenzenesulfonate
After stirring and mixing, use a homogenizer for 10 minutes.
Dispersion was performed at 1000 rpm.

Polymer dispersion method 30 mmol of reducing agent (I) or compound of the invention and PM
7.5 g of MA was dissolved in 40° C. of ethyl acetate at about 60° C. to form a homogeneous solution. 1 of this solution and lime-treated gelatin
100g of 0% aqueous solution and 5 of surfactant with the following structure.
% solution 6.7-, and then dispersed with a homogenizer at 11,000 rpm for 10 minutes.

The mixture was ground for 20 minutes. Glass peas were separated by mouth to obtain an aqueous dispersion.

Example 2 In Photosensitive Material 1 of Example 1, the reducing agent and the compound of the present invention were dispersed in gelatin in the second and fourth layers by an oil dispersion method as shown in Table 4. 12
It was created.

These light-sensitive materials were exposed to light and heat-developed in the same manner as in Example 1, and the resulting spectrum duram had ? of each color. The results of measuring H degrees are shown in Table 5.

The reducing agent used is shown below.

Fine particle dispersion method reducing agent (I) or the compound of the present invention! l! By adding 20 mmol of 1ff and 0.5 g of aerosol OT to 100 g of 1% gelatin aqueous solution, and further adding 100 g of glass beads having an average particle size of about 0.6 m + m, the compound of the present invention is used in combination with a reducing agent from Table 4. It was found that color reproduction was further improved and images with high density could be obtained.

Claims (1)

[Scope of Claims] Thermal development comprising, on a support, at least a photosensitive silver halide emulsion, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound that releases a diffusible dye when reduced. The color photosensitive material is characterized by having a substantially non-photosensitive intermediate layer containing at least one compound represented by the following general formula (I) between two photosensitive layers having different color sensitivities. A heat-developable color photosensitive material. General Formula (I) A■Time■_tX In the formula, A means a redox mother nucleus, and is an atomic group that makes it possible to release ■Time■_tX by being oxidized during development processing. Time represents a tanning group connected to A using S, N, O or Se, and t represents an integer of 0 or 1. X represents a group that functions as a development inhibitor after being released from ■Time■_tX.