JPH0827529B2 - Photothermographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photothermographic material, and in particular, provides a positive image having a sufficient image density and a low minimum density in a short developing time.

(Prior Art and Problems) Photothermographic materials are known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-Silver Salt Photograph Edition (1982, published by Corona Publishing Co.). Page ~ 255
Page, U.S. Pat. No. 4,500,626 and the like.

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

For example, in U.S. Pat.No. 4,559,290, a so-called DRR compound is made to coexist with an oxidizing compound having no dye-releasing ability together with a reducing agent, and the reducing agent is oxidized by thermal development depending on the exposure amount of silver halide and is not oxidized. It has been proposed to reduce the residual diffusing agent to release a diffusible dye. In addition, European Patent Publication No. 220,746, Technical Report 87-6,199
(Open Technical Report Vol. 12, No. 22) describes a heat development positive image forming method using a novel compound which releases a diffusible dye by a similar mechanism.

In the positive image forming method as described above, the reducing agent is oxidized by reducing silver halide in the exposed area, but when the developing time is short, the reducing agent left unoxidized in the exposed area is exposed. Reducing a reducing dye-donor compound,
There was a drawback that caused an increase in the minimum concentration.

(Object of the Invention) It is an object of the present invention to provide a positive image forming photothermographic material which can obtain a sufficient image density and a low minimum density in a short developing time.

(Structure of the Invention) The object of the present invention is to provide at least a surface latent image type silver halide, a binder, an electron transfer agent or its precursor, an electron donor, and a diffusible dye which is reduced by the electron donor on a support. A photothermographic material comprising a reducible dye-donating compound capable of releasing a dye and a hydrazine derivative represented by the following general formula (I).

In formula (I) Y-NHNH-CHO, Y represents an aliphatic group, an aromatic group or a heterocyclic group.

In the general formula (I) 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 aryl group, such as a phenyl group and a naphthyl group.

The heterocycle of Y is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring or may be another aromatic group. A condensed ring may be formed with the ring or the hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, for example, a pyridine group, an imidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group,
A thiazolyl group and a benzthiazolyl group are preferred.

Y may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio. Group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, nitro group Groups, alkylthio groups, arylthio groups and the like.

When possible, these groups may be linked to each other to form a ring.

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

It is preferable that Y contains a ballast group that is commonly used in a non-moving photographic additive such as a coupler.

The ballast group is a compound represented by the general formula (I):
An organic group that gives a molecular weight sufficient to prevent diffusion into other layers, and is an alkyl group, aryl group, heterocyclic group, ether group, thioether group, amide group, ureido group, urethane group, sulfonamide. A combination of one or more groups such as groups. These groups may have a substituent, and as the substituent, those enumerated as the substituents of Y can be applied.

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

Y may have X ₀ L _{0 m0} , which is a group that promotes adsorption of the compound represented by formula (I) on the surface of silver halide grains.

Here, X ₀ is an adsorption promoting group on silver halide, and L ₀ is a divalent linkage. m ₀ is 0 or 1.

Preferred examples of the adsorption accelerating group represented by X ₀ on silver halide include a thioamide group, a mercapto group, a group having a disulphide bond and a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by X ₀ is 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. 5, No. 4,031,127, No. 4,080,207, No. 4,254,037,
No. 4,255,511, No. 4,266,013, and No. 4,276,364,
And "Research Disclosure" (Research
Disclosure) Volume 151, No. 15162 (November 1976), and Volume 176, No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, a dithiocarbamate group, and a specific example of the cyclic thioamide group.
For example, 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiovidantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4
Triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline- 2-thione and the like, which may be further substituted.

The mercapto group of X ₀ is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship with this Synonymous with the 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 ₀ is composed of a combination of nitrogen, oxygen, sulfur and carbon.
And a 6- to 6-membered nitrogen-containing heterocycle. 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 appropriate substituents.

Examples of the substituent include those mentioned as the substituent of Y.

Examples of the divalent linking group represented by L ₀ include C, N, S,
An atom or atomic group containing at least one of O.
Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S-, -NH-,-
N =, —CO—, —SO ₂ — (these groups may have a substituent), etc., alone or in combination.

Among those represented by the general formula (I), preferred are those represented by the general formula (II).

General formula (II) (Y ₁ -L _{2 l} L ₁ -NHNH-CHO In the formula, L ₁ represents an arylene group, L ₂ represents a divalent linking group, and Y ₁ represents an aliphatic group or an aromatic group. Represents L ₁ , L
₂ The total number of carbon atoms in Y ₁ is 12 or more. l represents 0 or an integer of 1 to 3.

The arylene group represented by L ₁ is a phenylene group,
A naphthylene group is preferable, and a phenylene group is particularly preferable.
L ₁ may have a substituent, and as the substituent, those enumerated for Y in the general formula (I) can be applied in addition to Y ₁ -L ₂ —.

The divalent linking group represented by L ₂ is an atom or atomic group containing at least one of C, N, S and O.

Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, (R ₀₀ is a hydrogen atom, a straight chained, branched, or cyclic substituted or unsubstituted alkyl group having 30 or less carbon atoms, or a carbon number
It represents a substituted or unsubstituted phenyl group or naphthyl group of 30 or less. ), --N =, --CO--, --SO _2- , etc., or a combination thereof, and specifically, for example, --CH _2- , CH _{2 2} -CONH -, - OCONH -, - NHCONH-, -SCONH -, - SO 2 NH -, - NHSO 2 NH-, _{-CH 2 CH 2 SO 2 NH -} , - CH 2 CH 2 -O-CH 2 CH 2 - -CH 2 CH 2 NHCONH -, - CH 2 CH 2 -CONH- , and the like. These may be further substituted with an appropriate substituent, and as the substituent, those enumerated for Y in the general formula (I) can be applied.

The aliphatic group represented by Y ₁ is a substituted or unsubstituted direct or branched or cyclic alkyl group having 70 or less carbon atoms, preferably 30 or less, an alkenyl group, an alkynyl group,
It is preferably a branched or cyclic alkyl group.

The aromatic group represented by Y ₁ preferably has 6 to 70 carbon atoms.
Is a substituted or unsubstituted aryl group.

As the substituent of Y ₁ , those enumerated for Y in the general formula (I) can be applied.

When 1 is 2 or 3, Y ₁ -L _2- may be the same or different. 1 is preferably 1 or 2.

L _1, L _2, the total number of carbon atoms of Y ₁ are to preferably 12 to 70, more preferably to 12 no sum of L _1, L _2, Y ₁ number of carbon atoms
70.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

The above-mentioned hydrazine derivative is a known compound and can be easily synthesized by a known method.

The hydrazine derivatives may be used alone or in combination of two or more.

The layer to which such a compound is added may be any layer in a photothermographic material (hereinafter, may be abbreviated as a photosensitive material), but the photosensitive layer or its adjacent layer (for example, an intermediate layer, A protective layer) is preferable, and a photosensitive layer is particularly preferable.

The addition amount is from 10 ^-9 to 1 mol of photosensitive silver halide.
The amount may be 10 ⁻³ mol, preferably 10 ⁻⁸ to 10 ⁻⁴ mol.

When the nucleating agent of the present invention is used in an excessively large amount, the maximum density is lowered, but by adding it in 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 a binder and a silver halide emulsion together with an electron transfer agent and an electron donor to form a single photosensitive layer. The reducible dye-donating 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, the layer of the reducible dye-donating compound is preferably located under the silver halide emulsion layer in terms of sensitivity. In this case, the electron transfer agent and the 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 such photosensitive layers are used. Usually, in order to reproduce full color, three sets of photosensitive layers having different color sensitivity are provided. For example, there are a combination of three sets of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of three sets of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can have various arrangement orders known for a conventional color light-sensitive material. Further, each of these color-sensitive layers may be divided into two or more layers if necessary.

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

The reducible dye-donating compound used in the present invention is preferably a compound represented by the following general formula [CI].

PWR- (Time) _t -Dye General formula [CI] In the formula, PWR is reduced by-(Time) _t -Dy.
Represents a group that releases e.

Time represents a group that is released from PWR as − (Time) _t −Dye and then releases Dye through the subsequent reaction.

 t represents an integer of 0 or 1.

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

In addition, SO _2-in one molecule described in Japanese Patent Application No. 62-106885
X (where X represents oxygen, sulfur or nitrogen) and a compound having an electron-withdrawing group, PO-X bond in one molecule described in Japanese Patent Application No. 62-106895 (where X is as defined above) And a compound having an electron-withdrawing group, which has a CX 'bond (X' is synonymous with X or represents -SO _2- ) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106887. Compounds.

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

General formula (CII) (Time _t Dye binds to at least one of R ¹⁰¹ , R ¹⁰² or EAG.

The portion of the general formula [CII] corresponding to PWR will be described.

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

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

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

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

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

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

 An enzyme is particularly preferable as X.

 The EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula (CI
Among the compounds represented by I), those represented by the general formula (CIII) are preferable.

General formula (CIII) (Time _t Dye binds to at least one of R ₁₀₄ and EAG.

 X has the same meaning as above.

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

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

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

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

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

Z ₂ -Z ₈ are -O -, - S-, or -SO ₂ - represents, Sub each is a single bond (pi bond), represents a substituent that describes a hydrogen atom or less. Subs may be the same or different, and may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocycle or heterocycle.

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

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

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

Time is based on the cleavage of the nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bond as a scratch, and the Dye
Represents a group that releases

Various groups represented by Time are publicly known, and for example, JP-A-61-61
-147244 (5)-(6), 61-236549 (8) -page, and Japanese Patent Application No. 61-88625 (36)-(44).

The dyes represented by Dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl groups, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dyes can also be used in the form of a temporarily shortened wave capable of producing multiple colors during development.

Specifically, Dye disclosed in EP 76,492A and JP-A-59-165054 can be used.

The compound represented by the above general formula [CII] or [CIII] is required to be immobile in the photographic layer itself, and therefore, the position of EAG, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁴ or X (especially EAG) is required. It is desirable to have a ballast group having 8 or more carbon atoms at the position (1).

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

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

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

The present invention uses an electron donor and an electron transfer agent (ETA), and details of these compounds are disclosed in European Patent Publication.
220746A2, Open Technical Report 87-6199, etc.
Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula [C] or [D].

General formula [C] General formula [D] In the formula, A ₁₀₁ and A ₁₀₂ each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected by a nucleophile.

 Here, as the nucleophile, OH , RO (R; alkyl
Groups, aryl groups, etc.), hydroxamic acid anions SO₃ ²
Anionic reagents such as or primary or secondary amines,
Hydrazine, hydroxylamines, alcohols,
Compounds with lone pairs such as alls
It

Preferred examples of A ₁₀₁ and A ₁₀₂ are a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
It may be a dialkylphosphoryl group, a diarylphorforyl group, or a protecting group disclosed in JP-A-59-197037 and 59-20105, and A ₁₀₁ and A ₁₀₂ are R ²⁰¹ if possible. , R ²⁰² , R ²⁰³ and R ²⁰⁴ may be bonded to each other to form a ring. Also, A ₁₀₁ and A ₁₀₂ may be the same or different.

R ²⁰¹ , R ²⁰² , R ²⁰³ and R ²⁰⁴ 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 imide. Represents a group, a carboxyl group, a sulfonamide group and the like. These groups may have a substituent if possible.

However, the total carbon number of R ^{201 to} R ²⁰⁴ is 8 or more. Further, in the general formula [C], R ²⁰¹ and R ²⁰² and / or
R ²⁰³ and R ²⁰⁴ are represented by R ²⁰¹ and R ²⁰² , R in the general formula [D].
²⁰² and R ²⁰³ and / or R ²⁰³ and R ²⁰⁴ may combine with each other to form a saturated or unsaturated ring.

Among the electron donors represented by the above general formula [C] or [D], those in which at least two of R ^{201 to} R ²⁰⁴ are substituents other than hydrogen atom are preferable. Particularly preferred compounds are those in which at least one of R ²⁰¹ and R ²⁰² and at least one of R ²⁰³ and R ²⁰⁴ are a substituent other than a hydrogen atom.

A plurality of electron donors may be used in combination, or an electron donor and a precursor thereof may be used in combination.

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

The amount of the electron donor (or its precursor) used is in a wide range, but preferably 0.01 per mol of the positive dye-donating substance.
A preferred range is from about mol to 50 mol, especially from about 0.1 mol to 5 mol. The amount is 0.001 to 5 mol, preferably 0.01 to 1.5 mol, per mol of silver halide.

As the ETA used in combination with these electron donors, any compound can be used as long as it is a compound that is oxidized by silver halide and the oxidant has the ability to cross-oxidize the electron donor. It is desirable that it be mobile.

Particularly preferred ETA has the following general formula [XI] or [XI
It is a compound represented by I].

In the formula, R represents an aryl group. R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁴ ,
R ³⁰⁵ and R ³⁰⁶ represent a hydrogen atom, 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.
These may be the same or different.

In the present invention, the compound represented by the general formula [X-II] is particularly preferable. In the general formula [X-II], R ³⁰¹ , R
³⁰² , R ³⁰³ and R ³⁰⁴ 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, and more preferably a hydrogen atom or a methyl group. , A phenyl group substituted with a hydrophilic group such as a hydroxymethyl group, a phenyl group or a hydroxyl group, an alkoxy group, a sulfo group, and a carboxyl group.

 The following are specific examples of ETA.

The ETA precursor used in the present invention does not have a developing action during storage of the photosensitive material before use, but the ETA is first activated by a suitable activator (for example, a base, a nucleophile, etc.) or an action such as heating. It is a compound that can be released.

In particular, the ETA precursor used in the present invention does not have a function as ETA before development because the reactive functional group of ETA is blocked by a blocking group, but it may be heated under alkaline conditions or by heating. It can function as an ETA because the blocking group is cleaved.

As the ETA precursor used in the present invention, for example, 1-
2 and 3-acyl derivatives of phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, metal salts (such as lead, cadmium, calcium and barium) of hydroquinone and catechol, acyl halide derivatives of hydroquinone, and oxazines of hydroquinone And bisoxazine derivatives, lactone-type ETA precursors, 4
Hydroquinone precursors having a quaternary ammonium group, cyclohex-2-ene-1,4-dione type compounds, compounds that release ETA by an electron transfer reaction, compounds that release ETA by an intramolecular nucleophilic substitution reaction, phthalides Examples thereof include an ETA precursor blocked with a group, and an ETA precursor blocked with an indomethyl group.

The ETA precursor used in the present invention is a known compound, for example, U.S. Patent Nos. 767,704, 3,241,967, 3,246,988, 3,295,978, 3,462,266,
No. 3,586,506, No. 3,615,439, No. 3,650,749
No. 4,209,580, No. 4,330,617, No. 4,310,61
No. 2, UK Patent Nos. 1,023,701, 1,231,830,
No. 1,258,924, No. 1,346,920, JP-A-57-40245,
58-1139, 58-1140, 59-178458, 59-182449
And JP-A-59-182450 can be used.

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

 ETA and an ETA precursor can be used in combination.

In the present invention, the combination of the electron donor and ETA is preferably incorporated in the photothermographic material. The electron donor, ETA or their precursors can be used in combination of two or more, respectively, and the emulsion layer (a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, an infrared-sensitive layer, an ultraviolet-sensitive layer, etc.) in the light-sensitive material is used. It can be added to each or only some of the emulsion layers,
Further, it can be added to an emulsion adjacent layer (an anti-halation layer, an undercoat layer, an intermediate layer, a protective layer, etc.), or can be added to all layers. The electron donor and ETA can be added to the same layer or to different layers. In addition, these reducing agents can be added to the same layer as the dye-donating substance or to another layer, but the diffusion-resistant electron donor is preferably present in the same layer as the dye-donating substance. preferable. ETA can be incorporated in the image receiving material (dye fixing layer), or when a trace amount of water is present during heat development, it may be dissolved in this water. The electron donor, ETA or their precursor is preferably used in a total amount of 0.01 to 50 mol, preferably 0.1 to 5 mol, per 1 mol of the dye donating substance.
The total amount is 0.001 to 5 mol, preferably 0.01 to 1.5 mol, based on 1 mol of silver halide.

Also, ETA accounts for 60 mol% or less, preferably
0 mol% or less. When ETA is dissolved in water and supplied, the concentration of ETA is preferably 10 ^-4 mol / l to 1 mol / l.

A reducing substance, a dye-donating substance, an electron donor of the present invention,
In order to introduce an electron transfer agent or a precursor thereof and other hydrophobic additives into the hydrophilic colloid layer, a high boiling organic solvent such as an alkyl phthalate ester (dibutyl phthalate, dioctyl phthalate, etc.), a phosphate ester (diphenyl ester) is used. Phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citrate ester (eg acetyl citrate tributyl), benzoate ester (eg octyl benzoate) , Alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (eg tributyl trimesate) Japanese Patent Application No. 61-231
No. 500 carboxylic acids, JP-A-59-83154, JP-A-59-17
8451, 59-178452, 59-178453, 59-178454
No. 59-178455, using the method described in U.S. Pat.No. 2,322,027 using the compounds described in the same 59-178457,
Or an organic solvent having a boiling point of about 30 ° C. to 160 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. After dissolving,
Dispersed in hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. After the dispersion, the low boiling point organic solvent may be removed by ultrafiltration or the like, if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donor substance used.
It is less than or equal to g. Further, it is 5 g or less, preferably 2 g or less, relative to 1 g of the diffusion resistant reducing agent. Further, 1 g or less of the high boiling point organic solvent, preferably 0.5 g or less, and more preferably 0.3 g or less is suitable for 1 g of the binder. In addition, Tokiko Sho 51-39853
The dispersion method using a polymer described in JP-A-51-59943 can also be used. Alternatively, it may be dispersed directly in the emulsion, or may be dissolved in water or alcohol and then dispersed in gelatin or the emulsion.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. (For example, methods described in JP-A-59-174830, JP-A-53-102733, and Japanese Patent Application No. 62-106882) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants are used be able to. For example, JP-A-59-1
The surfactants listed on pages (37) to (38) of 57636 can be used.

The photothermographic 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 further, 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 reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but it may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

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

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

The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsion used in the present invention 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 surface of a grain, and is also called a negative type emulsion. The definition of the surface latent image type emulsion is described in JP-B-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. Particle size is 0.1 ~
2μ, particularly 0.2 to 1.5μ is preferable. The crystal habit of the silver halide grains may be cubic, octahedron, tetrahedron, tabular with a high aspect ratio, or the like.

Specifically, U.S. Pat.No. 4,500,626, column 50, 4,6,6
No. 28,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), JP-A-62-253159 and the like can be used any of the silver halide emulsions.

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

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

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

Organic compounds that can be used to form the above organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolic acid described in JP-A-60-113235 and acetylene silver described in JP-A-61-290444 are also useful. Two or more kinds of organic silver salts may be used in combination.

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

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

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

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

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

Along with a sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). No., Japanese Patent Application No. 61-226294, etc.).

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

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

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

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

The constituent layers (including the backing layer) of the light-sensitive material or the dye-fixing material include various polymers for the purpose of improving physical properties of the film such as dimensional stability, curling prevention, adhesion prevention, film crack prevention, and pressure sensation. Latex can be included. Specifically, JP-A Nos. 62-245258, 62-136648, and 62-
Any of the polymer latexes described in No. 110066 and the like can be used. In particular, when polymer latex with a low glass transition point (40 ° C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when polymer latex with a high glass transition point is used for the back layer, curl is prevented. The effect is obtained.

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

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a light-sensitive material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or in the form of being coated on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-161.
88256, mordanting agents described on pages (32) to (41), JP-A-62-
Nos. 244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

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

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

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

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

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

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

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

As the metal complex, U.S. Pat. Nos. 4,241,155 and 4,2
45,018 No. 3 to 36, No. 4,254,195, No. 3 to 8, Japanese Patent Application Laid-Open No. 62-174741, 61-88256 (27) to (29), Japanese Patent Application No. 62-234103, 62. -31096 and Japanese Patent Application No. 62-230596.

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

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

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

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

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

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

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

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
No. 62-135826 and the like, or fluorine-based surfactants such as fluorine-containing compounds such as fluorine-containing compounds, or hydrophobic fluorine such as solid fluorine-containing compounds such as tetrafluoroethylene resin. Examples include elementary compounds.

A matting agent can be used for the light-sensitive material and the dye-fixing material. As the matting agent, in addition to the compounds described in JP-A No. 61-88256 (page 29) such as silicon dioxide, polyolefin or polymethacrylate, Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like. No. 62-110065.

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

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

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

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

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

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

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

As the support of the light-sensitive material or dye fixing material of the present invention,
A material that can withstand the processing temperature is used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and polypropylene etc. Film synthetic paper made from, synthetic paper made from synthetic resin pulp such as polyethylene and natural parop, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. Used.

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

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

The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agent.

Examples of the method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of using a copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode, various lasers, etc. via electrical signals, CRT, liquid crystal display, electroluminescence There is a method of outputting to an image display device such as a sense display or a plasma display and exposing directly or via an optical system.

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

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

Further, the image information is an image signal obtained from a video camera, an electronic styryl camera or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into a large number of pixels such as a scanner. Signal, CG, CAD
An image signal created by using a computer represented by

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

The heating temperature in the heat development step is about 50 ° C. to about 25 ° C., but about 80 ° C. to about 180 ° C. is particularly useful. The dye transfer process may be performed at the same time as the heat development, or may be performed after the end of the heat development process. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

The migration of the dye occurs only by heat, but a solvent may be used to promote the dye migration.

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

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

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

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

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

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are oximes and other heterocycles.

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

The heating method in the development and / or transfer step may include contact with a heated block or plate, contact with a hot plate, a hot press, a heat roller, a halogen lamp heater, an infrared and far infrared lamp heater, or a high temperature. There is a passage through the atmosphere.

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

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

〔Example〕

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

Example 1 (1) Preparation of silver halide emulsion Emulsion (I) Sodium chloride and potassium bromide were added to a well-stirred aqueous gelatin solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C.). An aqueous solution containing 600 ml of silver nitrate and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate was dissolved) were simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μ was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.

Emulsion (II) 600 ml of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75 ° C) and an aqueous solution of silver nitrate (water). Dissolve 0.59 mol of silver nitrate in 600 ml) and the following dye solution (I) at the same time 40
An equal flow rate was added over the course of a minute. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having a dye having an average particle size of 0.35 μ adsorbed was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.

Dye solvent (I): 160 mg of sensitizing dye (I) dissolved in 400 ml of methanol.

Sensitizing dye (I) Emulsion (III) 1000 ml of an aqueous solution containing potassium iodide and potassium bromide in a well stirred gelatin aqueous solution (20 g of gelatin and ammonium dissolved in 1000 ml of water and kept at 50 ° C) and an aqueous solution of silver nitrate (water). (1 mol of silver nitrate dissolved in 1000 ml) was simultaneously added while keeping the pAg constant. In this way, a monodisperse octahedral silver iodobromide emulsion having an average grain size of 0.5 μm (bromine: 1.6 mol%) was prepared.

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

(2) Preparation of gelatin dispersion of dye-donor compound (I) Gelatin dispersion of yellow dye-donor compound Yellow dye-donor compound [Exemplary compound (1) described in the text] 13 g, high-boiling organic solvent ( 1) 6.5 g, electron donor [exemplified compound (ED-1) described in the text, hereinafter electron donor ED-1
Say. ] 6.5g was added to cyclohexanone 37ml and dissolved,
100 g of a 10% gelatin solution and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes.

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

(II) Gelatin dispersion of magenta dye-donor compound 16.8 g of magenta dye-donor compound [exemplified compound (2) described in the text], 8.4 g of high-boiling organic solvent (1), electron donor (ED-1) Add 6.3 g to cyclohexanone 37 ml and dissolve,
100 g of a 10% gelatin solution and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were mixed by stirring, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of the magenta dye-donor compound.

(III) Gelatin dispersion of cyan dye-donor compound 15.4 g of cyan dye-donor compound [Exemplified compound (3) described in the text], high-boiling organic solvent (1) 7.7 g, electron donor (ED-1) Add 6.0 g of cyclohexanone to 37 ml and dissolve,
100 g of a 10% gelatin solution and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a cyan dye-donor compound dispersion.

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

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

Water-soluble polymer (1) Sumika gel L-5 (H) Sumitomo Chemical Co., Ltd. Water-soluble polymer (2) Surfactant (1) Aerosol OT Surfactant (2) Surfactant (3) Surfactant (4) Hardener (1) 1,2-Bis (vinylsulphonylacetamido) ethane High boiling point organic solvent (1) Tricyclohexylphosphate electron transfer agent (1) Exemplified compound (X-2) electron transfer agent Precursor (1) Sensitizing dye (II) Reducing agent (1) Exemplified compound (ED-7) Antifoggant (1) Antifoggant (2) Antifoggant (3) In the light-sensitive material 1, the compound of the present invention is contained in each of the first layer, the third layer and the fifth layer as shown in Table 3 in an amount of 5.0 × 10 ^-7 mol per mol of silver halide. Thus, light-sensitive materials 2 to 6 were prepared.

(3) Preparation of dye fixing material Each layer having the constitution shown in Table 2 was applied on a paper support laminated with polyethylene to prepare a dye fixing material.

The additives used are shown below.

Silicone oil Surfactant (1) Aerosol OT Surfactant (2) Surfactant (3) Polymer Vinyl alcohol Sodium acrylate copolymer (75/25 molar ratio) Dextran (molecular weight 70,000) Mordant High boiling point organic solvent Leofos 95 (manufactured by Ajinomoto Co., Inc.) Hardener Matting agent Benzoguanamine resin Average particle size 10μm A tungsten light bulb is used for the color light-sensitive material of the above multi-layered structure, and the density is continuously changed, and it is exposed at 4000 lux for 1/10 seconds through B, G, R and gray color separation filters. did.

While feeding the exposed light-sensitive material at a linear velocity of 20 mm / sec, 15 ml / m ² of water was supplied to the emulsion surface with a wire bar, and immediately thereafter, they were superposed so that the dye-fixing material and the film surface were in contact with each other.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film became 85 ° C. Then, the photosensitive material was peeled off from the dye fixing material, and B, G, and R were placed on the dye fixing material.
Images of blue, green, red and gray were obtained corresponding to the and color separation filters of gray.

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

From the results shown in Table 3, it can be seen that the light-sensitive material using the compound of the present invention has a low minimum density without impairing the maximum density.

Claims (1)

[Claims] 1. A reducible material which releases at least a surface latent image type silver halide on a support, a binder, an electron transfer agent or a precursor thereof, an electron donor, and a diffusible dye when reduced by the electron donor. A photothermographic material comprising a dye-donating compound and a hydrazine derivative represented by the following general formula (I). In formula (I) Y-NHNH-CHO, Y represents an aliphatic group, an aromatic group or a heterocyclic group.