JPH0216539A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To lower the min. density without impairing the max. density by incorporating a photosensitive silver halide, binder, electron transmitting agent, electron donor, reducible dye-donating compd. which is reduced by the electron donor to release a dye, and hydrazine deriv. onto a base. CONSTITUTION:This photosensitive material contains at least the surface latent image type silver halide, the binder, the electron transmitting agent or the precursor thereof, the electron donor, the reducible dye-donating compd. which is reduced by the electron donor to release the diffusive dye, and the hydrazine deriv. The hydrazine deriv. expressed by the formula I is preferable. In the formula I, Y denotes an aliphat. group, arom. group or heterocyclic group. Both A1, A2 are a hydrogen atom or one thereof is the hydrogen atom and the other denotes an alkyl sulfonyl group, aryl sulfonyl group. R denotes a hydrogen atom, alkyl group, etc.; G denotes a carbonyl group, sulfonyl group, etc. The sufficient image density and the low min. density are obtd. in a short period of development time in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat-developable photosensitive material, and particularly to a material that provides a positive image with sufficient image density and a low minimum density in a short development time.

(Prior Art and Problems) Heat-developable photosensitive materials are well known in this field, and for information about heat-developable photosensitive materials and their processes, see, for example, 24 of ``Fundamentals of Photographic Engineering'' Non-Silver Salt Photography km (published by Corona Publishing, 1982).
Pages 2 to 255, US Pat. No. 4,500,626, etc.

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

For example, in U.S. Pat. No. 4,559,290, the so-called D
An oxidized version of the RR compound that does not have the ability to release dye is made to coexist with a reducing agent, and the reducing agent is oxidized according to the amount of sunlight on the silver halide through heat development, and the remaining unoxidized reducing agent is used to reduce the A method has been proposed in which a diffusible dye is released. Also, European Patent Publication No. 220,746, Publication Branch 87-6, 199 (Publication Branch, Vol. 12, No. 22)
describes a method for forming a heat-developable positive image using a novel compound that releases a diffusible dye by a similar mechanism.

In the positive image forming method as described above, in the exposure section,
The reducing agent is oxidized by reducing silver halide, but if the development time is short, the reducing agent remaining unoxidized in the exposed area reduces the reducible dye-donating compound, causing an increase in the minimum density. There were drawbacks.

(Object of the Invention) An object of the present invention is to provide a positive image-forming heat-developable photosensitive material that can provide a sufficient image density and a low minimum density in a short development time.

(Structure of the Invention) The object of the present invention is to provide a support with at least a photosensitive silver halide, a binder, an electron transfer agent, an electron donor, and a reducible material that releases a diffusible dye when reduced by the electron donor. This was achieved using a heat-developable photosensitive material containing a dye-providing compound and a hydrazine derivative.

The hydrazine derivatives used in the present invention include the following-
It is preferable to use the one shown in (mathematical formula).

- Formula (+) IAx In the formula, Y represents an aliphatic group, an aromatic group or a heterocyclic group. A, , Affi are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or -(C)-, Ro (wherein R0 is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or represents an aryloxy group, and n represents an integer of 1 or 2).

R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an azo group, or a heterocyclic group.

G is carbonyl group, sulfonyl group, sulfoxy group, -P
-1 or iminomethylene group.

However, a hydrazone structure <>NN=cg) may be formed by including G, A+, At, and hydrazine nitrogen.

In the general formula (1) of the present invention, the aliphatic group represented by Y is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group.

The aromatic group represented by Y is a monocyclic or bicyclic ring group, such as a phenyl group or a naphthyl group.

The heterocycle of Y is a 3 to 1 O membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, and these may be monocyclic or may include other rings. The heterocycle which may form a condensed ring with an aromatic ring or heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, such as a pyridine group, an imidazolyl group, a pyrimidyl group, a pyrazolyl group, inquinolinyl group,
A thiazolyl group, a benzthiazolyl group, etc. are preferred.

Y may be substituted with a substituent, and the substituent is
Examples include: These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryol group, alkylthio group, aryolthio group, sulfonyl group, sulfinyl group, hydroxy group,
Halogen atoms, cyano groups, sulfo groups and carboxyl groups,
Examples include aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, alkylthio group, and arylthio group.

These groups may be linked to each other to form a ring when possible.

Preferred as Y is an aromatic group, more preferably an aryl group.

Among the groups represented by R, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, etc.), aralkyl group (e.g., O-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3.5-dichlorophenyl group, O-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group) ), alkoxy groups (e.g., methoxy group, etc.), aryloxy groups (e.g., phenoxy group, p-nitrophenoxy group, p-chlorophenoxy group, etc.), amino groups (e.g., methylamino group, phenylamino group, p-chlorophenoxy group, etc.), -nitrophenylamino group, p-methoxyphenylamino group, etc.), alkoxycarbonyl group (
(e.g., ethoxycarbonyl group), carbonyl group (e.g., phenoxycarbonyl group), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, etc.), azo group (e.g., phenylazo group, etc.), It is a cyclic group (for example, a nitrogen-containing heterocyclic group such as a pyridyl group or a quinolyl group), and a hydrogen atom is particularly preferable.

Furthermore, when G is a sulfonyl group, R is an alkyl group (
For example, methyl group, etc.), aralkyl group (for example, 0-hydroxyphenylmethyl group, etc.), aryl group (for example, phenyl group, etc.), or substituted amino group (for example, dimethylamino group, etc.) are preferred.

When G is a sulfoxy group, R is preferably a cyanobenzyl group, a methylthiohensyl group, or the like.

When G is -P-, R is preferably a methoxy group, an ethoxy group, a butoxy group or a phenyl group, with a phenoxy group being particularly preferred.

When G is an N-substituted or unsubstituted imino methylene group, R is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

G is most preferably a carbonyl group.

As the substituent for R, the substituents listed for Y can be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may form a ring connected to each other.

Among Y and R1, Y preferably contains a ballast group which is commonly used in immobile photographic additives such as couplers.

The ballast group is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula (1) from diffusing into other layers or processing liquids, and includes an alkyl group, an aryl group, a heterocyclic group, and a ballast group. group, ether group, thioether group,
It consists of a combination of one or more of amide groups, ureido groups, urethane groups, sulfonamide groups, etc. These groups may have a substituent, and as the substituent, those listed as the substituent for Y can be applied.

When Y or R has a ballast group, the total number of carbon atoms in Y and R is preferably 12 or more.

Y or R is a group that promotes the adsorption of the compound represented by the general formula (I) onto the surface of silver halide grains;
2 sho of Li. It may have.

Here, X is an adsorption promoting group to silver halide, and Lo
is a divalent linkage 0m0 is 0 or 1.

Preferred examples of the adsorption-promoting group to silver halide represented by X include a thioamide group, a mercapto group, a group having a disphite bond, or a 5- to 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group boiled with X is a divalent group represented by C-amino-, and may be a part of a ring structure, or may be an acyclic thioamide group.

Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
No. 30,925, No. 4,031,127, No. 4,08
No. 0,207, No. 4,254,037, No. 4. 25
5. No. 511, No. 4,266.013, and No. 4,
No. 276.364, as well as “Research Disclosure J.
e) Magazine Volume 151 ll & 115162 (November 1976) and Volume 176S 17626 (1978
You can choose from those disclosed in December 2017).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc. Specific examples of cyclic thioamide groups include 4-thiazoline-2-thione, 4-imidacyline-
2-thione, 2-thiovidantoin, rhodanine, thiobarbylic acid, tetrazoline-5-thione, 1. 2
．． 4-triazoline-3-thione, 1.3.4-thiadiazoline-2-thousand, 1.3.4-oxadiazoline-2-thousand, benzimidacillin-2-thione, benzoxazoline-2- Thione and benzothiazoline
Examples include 2-thione, which may be further substituted.

The mercapto group of group, and specific examples of this group are the same as those listed above).

The 5- to 6-membered nitrogen-containing heterocyclic group represented by X is 5 consisting of a combination of nitrogen, oxygen, sulfur and carbon.
and 6-membered nitrogen-containing heterocycles. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine, and the like.

These may be further substituted with a suitable substituent.

Examples of the yA group include those described for the ice group of Y.

The divalent linking group represented by L is C1N, S,
An atom or atomic group containing at least one type of O.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O--3--NH--
N= -CO-3O* (these groups may have a substituent), etc., alone or in combination.

A 1 s A z is a hydrogen atom, an a/L/-1-JL/sulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's substituent constants of -0.5 or more) a phenylsulfonyl group substituted so that (phenyl group substituted as above), alkoxy group (for example, ethoxy group, etc.), aryloxy group (preferably monocyclic), etc. These groups may have a substituent. The substituents for Y include those mentioned above. ).

AI and AI are most preferably hydrogen atoms.

- Among those represented by formula (1), preferred are those represented by general formula (■).

-Formula (U) (yt t, xtoJ Lr N N G
In the R formula, AI, At, and GR have the same meanings as in the general formula (RI). Ll represents an arylene group,
L2 represents a divalent linking group, Yl represents an aliphatic group or an aromatic group, and the total number of carbon atoms of R, Lr, and Lx-Y is 12 or more. l represents 0 or an integer from 1 to 3.

The arylene group represented by L is a phenylene group,
A naphthylene group is preferred, and a phenylene group is particularly preferred e
Ll may have a substituent, and the substituent is Y+
In addition to Lm-, those listed for Y in general formula (1) can be applied.

L! The divalent linking group represented by is an atom or atomic group containing at least one of C, N, S, and 0.

Specifically, for example, an alkylene group, an alkenylene group,
Alkynylene group, arylene group, -0--3-N(R*
. represents a hydrogen atom, a straight, branched, or cyclic substituted or unsubstituted alkyl group having 30 or more carbon atoms, or a substituted, substituted or unsubstituted phenyl group or naphthyl group having 30 or less carbon atoms. , ), −N=
-GO--3o-containing-1, etc., alone or in combination, and specifically, for example, -CHl
-5-(CHt) z-CONH-1-0CONH-
1-NHCONH-1SCONH-1-8O□NH-1
-NH3O2N) (-1CHz CHt So□NH-
1 CHz CHz OCHt CH2--CH2Cl-
Examples include 1z NHCONH-1-CH2CH, -CONH, and the like. These may be further substituted with a suitable substituent, and as the substituent, those listed for Y in general formula (1) can be applied.

The aliphatic group represented by Yl is a substituted or unsubstituted straight, branched, or cyclic alkyl group, alkenyl group, or alkynyl group having 70 or less carbon atoms, preferably 30 or less carbon atoms, and preferably a branched or cyclic alkyl group. It is.

The aromatic group represented by Yl preferably has 6 to 7 carbon atoms.
0 substituted or unsubstituted aryl group.

As the substituent for YI, those listed for Y in general formula (+) can be applied.

When l is 2 or 3, Y IL z- may be the same or different. l is preferably 1 or 2.

The total number of carbon atoms of R, L+, L2, YI is preferably 12 to 70, more preferably Ll, L2, Y
The total number of carbon atoms in l is 12 to 70.

-G Specific examples of the compound represented by formula (1) are shown below.

However, the present invention is not limited to the following compounds.

○ H O The above hydrazine derivative is a known compound and can be easily synthesized by a known method.

One type of hydrazine derivative may be used alone, or two or more types may be used in combination.

The layer to which such a compound is added may be any layer in a heat-developable photosensitive material (hereinafter sometimes abbreviated as "photosensitive material"), but it may be added to the photosensitive layer or its adjacent layer (for example, an intermediate layer, protective layers, etc.) are preferred, and photosensitive layers are particularly preferred.

The amount added is 10-9 per mol of photosensitive silver halide.
~10-'' mol, preferably 101 to 10-4 mol.

If the nucleating agent of the present invention is used in too large a quantity, the maximum density will be lowered, but by adding it within the above range, the minimum density can be lowered without impairing the image density.

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 with different color sensitivities are required.For example, a combination of three sets of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. There are combinations of three sets of photosensitive layers, etc. Each color-sensitive layer can be arranged in various orders known for conventional color-sensitive materials.

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

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 formula (C-1).

PWR-(Time)t-Dy e-Formula (C-1
) where PWR is reduced to −(Time)
Represents a group that releases L-[)ye.

Time is from PWR -(Time) t
After being released as Dye, Dy
Represents a group that releases e.

t represents an integer of 0 or 1.

Dye represents a dye or its precursor.

First, PWH will be explained in detail.

PWR is U.S. Patent No. 4,139,389, or U.S. Patent No. 4,139.379, U.S. Patent No. 4,564.577,
Electron-accepting center and intramolecular nucleophilic substitution reaction in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-59-185333 and JP-A-57-84453 It may correspond to the part including the center, or it may correspond to the part including the center, or as described in 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,
884, in which the single bond is cleaved to release the photographic reagent, an aryl group substituted with an electron-withdrawing group and the atom connecting it to the photographic reagent (
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, This corresponds to the geminal dinitro moiety in the dinitro compound that desorbs the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in U.S. Pat. No. 4,609.610. It's okay.

In addition, compounds having SO□-X (X represents oxygen, sulfur, or nitrogen) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 106885/1982,
A compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 6895, patent application No. 62
-106887, which has a c-x' bond (X' is synonymous with X or represents -5O2-) and an electron-withdrawing group in one molecule.

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

- Formula (cm) EAG (Time) -t Dye combines with at least one of R1111, RlO2, or EAG.

-The part corresponding to PWR in formula [C■] will be explained.

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

RlO1, R1°2 and RI113 represent a group other than a hydrogen atom or a simple bond.

Examples of groups other than hydrogen atoms represented by R161, RlO2, and R103 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, and sulfamoyl groups, and these include substituted It may have a group.

RIOI and R103 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero-1,1, acyl groups, sulfonyl groups, and the like. R.I.
The number of carbon atoms in OI and R'03 is preferably 1 to 40.

R102 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group mentioned for R161 and RlO:1. The number of carbon atoms is preferably 1 to 40.

RIOI, Rlot and R1o's may be bonded to each other to form a 5- to 1-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 (CD)
Among the compounds represented by the formula, those represented by the general formula (CI[[) are preferred.

General formula (CI[[) (TimetwDye binds to at least one of RI114 and EAG.

X has the same meaning as above.

R11+4 represents an atomic group that is bonded to the nitrogen atom of X1 to form a monocyclic or condensed heterocycle of five or more members including the nitrogen atom.

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

-Formula (A) In general formula (A), Zl represents 10-3ub or -N-.

Blue represents an atomic group that forms an aromatic group with Z1%Z2, and n represents an integer from 3 to 3.

Vs;Zs-1v,i-ZS-Z,-1vS;Z
s Za Za-1Vh: Zs ZaZs
2&-1Vqi Zx Za Zs Z4-
Z, -1V*; z2 z4 Zs Za-z
It is t-zs-.

Each of Zx Za represents -C--N--Oub -S-2 or -8O8-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Subs may be the same or different, or may be bonded to each other to form two or more saturated or unsaturated carbocycles or heterocycles.

In general formula (A), the sum of the Hammett 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.

RAG is preferably a ring group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the heptalyl group or heterocyclic group of RAG can be used to adjust the physical properties of the entire chemical compound. Examples of physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, and reaction with nucleophilic groups. It can be used to adjust the properties, reactivity toward electrophilic groups, etc.

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

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

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244.
No. 36549 (8) p.-p., patent application No. 61-88625
Examples include the groups described on 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, EP76.492A, JP 59-165
Dye disclosed in No. 054 can be used.

The above-mentioned compound represented by the formula (C1l) or (CIII) must itself be non-migratory in the photographic layer, and for this purpose the compound at the EAC, R101, R1@2R164 or ) preferably has a ballast group having 8 or more carbon atoms.

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

(lO) C,,H,.

R: Hs C+5II2j Each of these compounds can be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-donating compound used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol/d, preferably 0.1 to 3 mmol/d.
It is in the mmol/d range. The dye-donating substances can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 51, mobile dyes having different hues, for example, at least one of cyan, magenta, and yellow dye-providing substances are mixed and contained in a layer containing silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of dye-providing substances that emit .

In the present invention, an electron donor and an electron transfer agent (ETA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Kokka Gibu No. 876199, and the like. A particularly preferred electron donor (or its precursor) is a compound represented by the following formula (C) or CD).

- Formula [C] General formula CD) In the formula, A1゜1 and A1゜ each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, as the nucleophile, 0HeXROe (R; alkyl group, aryl group, etc.), hydroxamic acid anion l
Examples include anionic reagents such as "so" and "e", and compounds having lone pairs of electrons such as primary or secondary amines, hydrazine, hydroxylamines, alcohols, and 1,000-ols.

AIor, A,. Preferred examples of 2 are hydrogen atoms,
Acyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoryl group, dialkylphosphoryl group, or JP-A-59-197037, JP-A-59-2
It may be a protecting group disclosed in No. 0105, or A
1°+, Al62 is R2°I, R when possible
20Z, R10'' and R204 may be combined with each other to form a ring.Also, A1.)A, .O may be the same or different.

Rffi61, Rlot, R2111 and R20
4 each represents 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 imide group, a carboxyl group, a sulfonamide group, etc. represent. These groups may have a substituent if possible.

However, the total carbon number of R201 to R204 is 8 or more. Moreover, in -i formula (C), R20I and R20
2 and/mata are Rto'a and R204 are - formula CD
), Rzo and l';jlO! , R202 and R2°3 and/or R2O3 and R2°4 may be bonded to each other to form a saturated or unsaturated ring.

Among the electron donors represented by formula (C) or (D), those in which at least two of R201 to Rto4 are substituents other than hydrogen atoms are preferred, and particularly preferred compounds are at least one of R201 and Rzot, and at least one of R2O3 and R2O3 is a substituent other than a hydrogen atom.

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

(ED-1) (ED-3> (ED (ED H3 (ED-2) H3 (ED-7) (ED-11) (ED (ED-9) (ED) of electron donor (or its precursor) The amount used has a wide range, but preferably 0.0 per mole of positive dye-providing substance.
A preferred range is from 1 mol to 50 mol, particularly from 0.1 mol to 5 mol. Also, 0.00% per mole of silver halide.
001 mol to 5 mol, preferably 0.001 mol to 5 mol. O1 mol ~ 1.5
It is a mole.

As the ETA used in combination with these electron donors, any compound can be used as long as it is oxidized by silver halide and the oxidized form thereof has the ability to cross-oxidize the above electron donor. Preferably a sexual one.

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

(X-1) (X-old formula, R represents an aryl group. R3111, R362R""ff,
R", R"O5 and HR36h hydrogen atom, halogen atom, acylamino group, alkoxy group, alkylthio group,
It represents an alkyl group or an aryl group, and may be substituted if possible. Further, in the present invention, these may be the same or different, and a compound represented by formula (X-11) is particularly preferred. - In formula (X-11), R
:lOl, Rff (12, R3°3 and R304 are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, 1 to 1 carbon atoms
10 substituted alkyl groups and substituted or unsubstituted aryl groups are preferred, and more preferred are hydrogen atoms, methyl groups,
Hydroquine is a methyl 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-3> (X-4) (X-9) (X-6) (X-8> (X-10) The PTA precursor used in the present invention is It is a compound that does not have a developing effect during storage of a photosensitive material before use, but can release ETA only by the action of a suitable activator (eg, base, nucleophile, etc.) or heating.

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

Examples of the ETA precursor used in the present invention include 1-
2- and 3-acyl derivatives of phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium, calcium, barium, etc.), acyl halide m8 of hydroquinone, hydroquinone Oxazine and bisoxazine derivatives, lactone-type ETA precursors,
Hydroquinone precursors with quaternary ammonium groups, cyclobequix-2-ene-1,4-dione type compounds, compounds that release ETA through electron transfer reactions, compounds that release ETA through intramolecular nucleophilic substitution reactions, 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, U.S. Pat.
, No. 967, 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. No. 749, No. 4,209,580, No. 4,330.617, No. 4,310,612
British Patent No. 1,023,701, British Patent No. 1.231
゜830, same No. 1.258,924, same No. 1゜34
6.920, JP-A-57-40245, JP-A-57-40245, JP-A No. 5B-1
No. 139, No. 58-1140, No. 59-178458
The developer precursors described in Japanese Patent No. 59-182449, Japanese Patent 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 the adjacent Jl of 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. Preferably, 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 usage amount of the precursor is 0.01 to 50 mol in total, preferably 0.1 mol per 1 mol of the dye-donating substance.
~5 mol, total amount 0.0 for 111 mol of halogenated
01 to 5 mol, preferably 0.01 to 1.5 mol.

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

In order to introduce the reducing substances, dye-donating substances, electron donors, electron transfer agents or their precursors and other hydrophobic additives of the present invention into the hydrophilic colloid layer, high-boiling organic solvents such as alkyl phthalates can be used. Esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid 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. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) Patent application 1987 -231500
Carboxylic acids described in JP-A-59-83154, JP-A-59178451, JP-A-59-178452, JP-A-59
-178453, 59-178454, 59-
178455 and 59-178457, using the method described in U.S. Pat. After dissolving in lower alkyl acetate such as ethyl propionate, secondary 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 organic solvent and 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. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing 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 or less of high boiling point organic solvent per 1 g of binder,
The amount is preferably 0.5 g or less, more preferably 0.3 g or less. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 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-59-174830, JP-A No. 53-1
02733, Japanese Patent Application No. 62106882, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, JP-A-59-
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 divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

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

For example, there are combinations of three layers such as 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 is also called a negative type emulsion. The definition of surface latent image type emulsion is described in Japanese Patent Publication No. 5B-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, or a mixture of monodisperse emulsions may be used. Particle size is 0.1~
2μ, especially 0.2 to 1.5μ is preferred. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other form.

Specifically, U.S. Patent No. 4,500,626 50g
, No. 4,628.021, Research Disclosure (hereinafter abbreviated as RD) 17029 (197
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Silver halide emulsions may be used unripe, but they are usually chemically sensitized before use. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing 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 g/rrl to 10 g/rrl 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 organic silver salt oxidizing agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044. 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. Ol to 10 moles, preferably 0°01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50cm to 10g10 in terms of silver.
f is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) 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.

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

Specifically, U.S. Pat.
17Q29 (1978), pages 12-13, and the like.

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

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. , No. 615゜641, patent application No. 61-22
6294 etc.).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in US Pat. No. 4.183.
It may be added before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666, and the amount added is generally about 10-0 to 104 mol per mol of silver halide.

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

Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, and polysaccharides such as starch, gum arabic, dextran, and pullulan.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, the super absorbent polymer described in JP-A-62-245260 etc., namely -COOM or -3OsM (
M is a hydrogen atom or an alkali metal) homopolymers of vinyl monomers or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (
Sumikagel L-58) manufactured by Co., Ltd. is also used. Two or more of these binders can also be used in combination.

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

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

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 61-110066, 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, dye fixing materials are used together with photosensitive materials. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500.626 can also be applied to the present application.

The dye fixing material preferably used in the present invention has at least 11 layers 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.
and mordants described in JP-A-61-88256, pages (32) to (41), JP-A-62-244043, JP-A-62-244043, and JP-A-62-244043;
Examples include those described in No. 244036 and the like.

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

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

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

In the constituent layers of the light-sensitive material and the dye-fixing material, a high boiling point a solvent can be used 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, especially carboxy-modified silicone (product name: X-2
2-3710) 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 phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. 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-46-2784, etc.), and other JP-A-54-48535 and JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, and the like.

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

As metal complexes, US Pat. No. 4,241,155,
4.245,018 No. 3-3641, 4.2
54,195 No. 3-8411, JP-A-62-1747
No. 41, No. 61-88256, pages (27) to (29),
Patent application No. 62-234103, No. 62-31096,
There are compounds described in Japanese Patent Application No. 62-230596.

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

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

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

A fluorescent brightener may be used in the light-sensitive material or dye-fixing material. In particular, it is preferable to incorporate the fluorescent brightener into the dye-fixing material or to supply it from outside the light-sensitive material.

Veenkataratsan &grThe Che
mistry of 5ynthetic Dyes J
Compounds described in Chapter V@Chapter 8, JP-A-61-143752, etc. can be mentioned. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat. No. 4,678.739, No. 414111;
Examples include hardeners described in JP-A-59-116655, JP-A-62-245261, and JP-A-61-18942. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-ethylene-bis(
(vinylsulfonylacetamide) etannat), 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,
Typical examples of organic fluoro compounds that may be included for the purpose of preventing static electricity, improving peelability, etc. are Japanese Patent Publication No. 57-9053, columns 8 to 17, and Japanese Patent Application Laid-Open No. 1983-1989.
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described 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. Wi image formation accelerators promote the oxidation-reduction reaction between silver salt oxidizing agents and reducing agents, promote reactions such as production of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and are useful in photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixed layer, and from a physicochemical function, it has a base or base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, 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. For more information on these see U.S. Patent 4.67.
No. 8,739, No. 38-40j7rA.

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.

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

In addition to the above, combinations of poorly soluble metal compounds and compounds capable of complexing reaction with metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

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

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

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with 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. triacetyl cellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin valves such as polyethylene, and natural paropn. 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, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black 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 the image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There is a method of outputting the image to an image display device such as a sense display or a plasma display and exposing it directly or through an optical system.

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

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as BaBx04,
Urea derivatives, nitroaniline derivatives, e.g. nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-
Compounds described in No. 53462 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 heat 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 process can be developed at about 0°C to about 25°C, but it is particularly useful to use a heating temperature of about 0°C to about 180°C.The dye diffusion transfer process is performed at the same time as the heat development. 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; More preferably, the temperature is up to about 1α°C lower than the temperature at .

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

Also, JP-A-59-218443, JP-A No. 61-2380
56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an 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 dye fixing materials, photosensitive materials, or both.

The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (particularly in mass sales, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film).

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, contact with a hot plate, hot presser, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. , passing through a high-temperature atmosphere, etc.

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

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-5975247, JP-A No. 59-177547, JP-A No. 59-181353, JP-A No. 6
(Apparatuses described in Japanese Utility Model Application No. 1-18951, Utility Model Application Publication No. 62-25944, etc. are preferably used.

〔Example〕

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

Example 1 A well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 100,100 O of water kept at 75°C) was charged with 600 mA of an aqueous solution containing sodium chloride and potassium bromide and an aqueous solution of silver nitrate (600 mA of water).
0.59 mol of nitric acid vA dissolved in n) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60° C. by adding 0.0 μm. The yield of emulsion was 600 g.

A gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 100,100 O of water and keeping it warm at 75°C) that has been soaked and stirred well in January is mixed with 600 mA of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (in water). 600m
11!0.59 mol of nitric acid dissolved in J+) and the following dye solution (Li) were simultaneously added at equal flow rates over 40 minutes.

In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) was prepared, in which a dye having an average grain size of 0.35 μm was adsorbed.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,? -Tetrazaindene 2
Chemical sensitization was performed at 60° C. by adding 0 Akebono. The yield of emulsion was 600 g.

Dye solution port)... Exacerbating pigment (+) 160 aw dissolved in 40 Oml of methanol.

Sensitizing dye (1) Add 11,000 ml of an aqueous solution containing potassium iodide and potassium bromide and a silver nitrate aqueous solution to a well-stirred gelatin aqueous solution (20 g of gelatin and ammonium dissolved in 10,100 O of water and kept at 50°C). (Water 1000mA
! 1 mole of silver nitrate dissolved in the solution) was added at the same time while keeping the pAg constant. In this way, a monodisperse octahedral silver iodobromide emulsion (1.6 mol % of bromine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, 5 parts of chloroauric acid (tetrahydrate) and 2 parts of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1 kg.

Several yellow dye-providing compounds (exemplary compounds listed in the text +
11) 13 g, 16.5 g of high boiling point organic solvent, 6.5 g of electron donor [exemplified compound (ED-1) described in the text, hereinafter referred to as electron donor ED-1), and cyclohexanone 3
Add and dissolve 100 g of 1O% gelatin I solution and 60 g of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate in 7 ml of
After stirring and mixing with m1, use a homogenizer for 10 minutes.
Dispersion was performed at 110,000 rpm.

This dispersion is called a yellow dye-providing compound dispersion.

(n) Magenta gelatin Several magenta dye-providing compounds [Exemplary compounds listed in the text (
2016.8 g, high boiling point organic solvent (118.4 g, electron donor (ED-1) 6.3 g, cyclohexanone 37 m
Add and dissolve 100 g of 10% gelatin solution, 60 g of 2.5% aqueous solution of sodium dodecylbenzenesulfonate.
m! After stirring and mixing, use a homogenizer for 10 minutes.
Dispersion was performed at 110,000 rpm. This dispersion is called a dispersion of a magenta dye-providing compound.

(I
l) 15. 4 g, high-boiling organic solvent (117,7
g, 6.0 g of electron donor (ED-1) and 37 mj of cyclohexanone! Add and dissolve 10% gelatin solution to 100%
g and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were stirred and mixed, and then mixed with a homogenizer for 10
Dispersion was performed at 110,000 rpm for 1 minute. This dispersion is called a dispersion of a cyan dye-providing compound.

Using the material thus prepared, a photothermographic material 1 having a multilayer structure shown in Table 1 was produced.

In addition, additives other than the above in Table 1 are shown below.

Water-soluble polymer +11 Sumikagel L-5 (H) Sumitomo Chemical Co., Ltd. water-soluble polymer (2) Phosphate electron transfer agent j11 Exemplary compound (X-2) described in the text
Electron transfer agent precursor (1) Surfactant ill Aerosol OT surfactant (2
) Sensitizing dye (n) Surfactant (3) Surfactant (4) Reducing agent (1) Exemplary compound described in the text (IED-7) Antifoggant +11 The following in Table 2 was applied on a paper support laminated with polyethylene. Each layer was applied according to the composition to create a dye-fixing material.

Table 2 Anti-fogging agent (2) Anti-fogging agent 3) In the photosensitive material 1 described above, the compounds of the present invention are added to the first layer, the third layer and the layer 511 as shown in Table 3, respectively. 6 was produced.

(3) Color ・No.1 The additives used are shown below.

Silicone oil Hs H3 (CHt)s C00II H3 Surfactant Tl) Aerosol OT Surfactant +21 Cm Fl? SO Mushroom NCHz
C00KsHq Surfactant (3) HI CuH2zCONHCHx CH! ChzN
'CHt Coo.

CHt Polymer Vinyl alcohol sodium acrylate copolymer C15/25 (mono-t-day-hi) Dextran (molecular weight 70,000) Mordant side hardener matting agent Benzoguanamine resin Average particle size 10 pm A tungsten light bulb is used in the above multilayered color photosensitive material , B whose concentration changes continuously.

400 through G, R and gray color separation filters
Exposure was made for 1/10 second at 0 lux.

While the exposed photosensitive material was being fed at a linear velocity of 20 w/see, 15 mj/ld of water was supplied to the emulsion surface using a wire bar, and then immediately superimposed so that the film surface was in contact with the dye fixing material.

When the zero-order photosensitive material heated for 15 seconds is peeled off from the dye-fixing material using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed film is 85°C, B,
Blue, green, red, and gray images were obtained corresponding to G, R, and gray color separation filters.

The maximum density (Dmax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part were measured. These results are shown in Table 3.

Table 3 From the results of Procedural Amendment Table 3, it can be seen that the light-sensitive materials using the compounds of the present invention have a lower minimum density without impairing the maximum density.

1゜

Claims (1)

[Claims] At least a surface latent image type silver halide, a binder, an electron transfer agent or its precursor, an electron donor, a reducible dye-donating compound that releases a diffusible dye when reduced by the electron donor, and A heat-developable photosensitive material comprising a hydrazine derivative.