JPH0823685B2 - Photothermographic material - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material having high sensitivity and excellent image density, and further having low fog when heat-developed. It is a thing.

Prior art and its problems Photothermographic materials are known in this technical field, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-Silver Photograph, 242, published by Corona Publishing Co., Ltd.
Pages-255 pages, 40 pages of video information issued in April 1978, Nebletts Handbook of Photography and R
eprography) 7th edition (7th Ed.) Van Nostrand Reinh
old Company) pages 32-33, U.S. Pat.Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075,
British Patent Nos. 1,131,108 and 1,167,777 and Research Disclosure, June 1978, pages 9-15 (RD-1
7029).

Many methods have already been proposed for obtaining a color image (color image) by heat development.

For the method of forming a color image by combining an oxidant of a developing agent and a coupler, U.S. Pat. No. 3,531,286, U.S. Pat.No. 3,761,270, Belgian Pat.No. 802,519, Research Disclosure, September 1975, pages 31-32 Page, U.S. Pat. No. 4,021,240 and the like.

For the method of forming a positive color image by the light-sensitive silver dye bleaching method, see, for example, Research Disclosure, April 1976, pp. 30-32 (RD-14433), 12: 1976.
Monthly pages 14 to 15 (RD-15227), U.S. Pat. No. 4,235,957 and the like.

Furthermore, a method of releasing a movable dye imagewise by heating and transferring the movable dye to a dye fixing material having a mordant with a solvent such as water, a method of transferring to a dye fixing material with a high boiling point organic solvent , A method of transferring to a dye-fixing material by a hydrophilic thermal solvent incorporated in the dye-fixing material, and a method of transferring to a dye-receiving material such as a support, in which the movable dye is heat diffusible or sublimable, have been proposed. (U.S. Pat.Nos. 4,463,0790, 4,474,867 and 4,4
No. 78,927, No. 4,507,380, No. 4,500,626, No. 4,
483,914; JP-A-58-149046, 58-149047, 59-
152440, 59-154445, 59-165054, 59-18054
No. 8, No. 59-168439, No. 59-174832, No. 59-174833,
59-174834, 59-174835, 59-218443, Japanese Patent Application No. 60-79709, etc.).

Various silver halide emulsions are known for use in heat development.

Since it is considered that the heat development of the silver halide emulsion for heat development proceeds in the manner of physical development, a design different from that of a so-called silver halide emulsion for wet processing is considered necessary. For example,
It can be said that the one capable of forming a latent image which becomes a physical development nucleus is effective, but the present situation is that no clear direction has been given to the design of the silver halide emulsion.

For this reason, thermal development has high sensitivity, a small fluctuation range of sensitivity due to fluctuation of temperature and humidity during exposure, a small range of sensitization or desensitization due to pressure, and a small fluctuation of photographic property during latent image progress and storage. No silver halide emulsion for use has been obtained yet.

By the way, in the photothermographic material, an auxiliary developing agent having a function of accelerating the development by intervening the reaction between the silver halide and the developing agent is used. Commonly known auxiliary developing agents include hydroquinone, t-butylhydroquinone, alkyl-substituted hydroquinones such as 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone. , Alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Further, hydroxylamines such as methyl oleate, ascorbic acid, ascorbic acid derivatives, N, N′-di- (2-ethoxyethyl) hydroxylamine,
Examples thereof include pyrazolidones such as 1-phenyl-3-pyrazolidone and 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, redarectones, and hydroxytetronic acids.

However, many of these auxiliary developing agents cannot be said to have a sufficient development accelerating effect, and even if they have a development accelerating effect, there are problems such as causing an increase in fog.

On the other hand, in the thermal development, fog which is unpredictable from usual wet development (processing in a developing solution) is often generated. In order to suppress this fog, various fog prevention techniques have been proposed.

For example, U.S. Pat. No. 3,589,903 describes that mercury compounds are effective in suppressing fog during thermal development, but it is not desirable to use such compounds harmful to the human body. Further, JP-A-60-198540 describes specific hydroquinone derivatives and 2,4-disulfonamidophenol derivatives, but these compounds do not have sufficient fog-preventing effect and have high sensitivity to halogen. There were drawbacks such as desensitization of silver halide emulsion.

II Object of the Invention The object of the present invention is to provide a photothermographic material that can obtain a highly sensitive and high-density dye image by heat development for a short time, reduce fog, and have other excellent photographic characteristics. To provide the material.

III Disclosure of the Invention Such an object is achieved by the present invention described below.

That is, the present invention is a photothermographic material having at least a silver halide emulsion, a reducing agent for the silver halide emulsion, and a binder on a support, wherein the silver halide emulsions are adjacent to each other in silver halide grains. One or more kinds of photosensitive silver halide grains having a multi-layer structure of at least three layers having different halogen compositions, and at least one layer having such a silver halide emulsion, And the following general formula (I) or (II)
A photothermographic material comprising at least one compound represented by:

General formula (I) General formula (II) {In the above general formulas (I) and (II), Ball is an organic ballast group capable of rendering the compounds represented by these formulas non-diffusible, and has a substituted or unsubstituted carbon number of 8 to 30. Alkyl group, acylamino group having 8 to 30 carbon atoms, acyl group having 8 to 30 carbon atoms, 8 carbon atoms
An acyloxy group having 30 to 30, an alkoxy group having 8 to 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, and an alkoxy group having 8 to 30 carbon atoms and an alkoxycarbonyl group having 8 to 30 carbon atoms A direct bond ballast group selected from the group, a carbamoyl group represented by the following formula (A) or a sulfamoyl group represented by the following formula (B).

(In the above formula, Ball 'represents the direct bond ballast group, R ³ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group or an aryl group, and L represents a divalent alkylene group or phenylene group. Alternatively, it represents a divalent arylthio group, and m represents 0 or 1. However, when R ¹ is a non-diffusible group, Ball may not be present.

Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus.

R ¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group.

R ² is a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group. Represents a group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group or an arylthio group.

n represents an integer of 0 to 5, and when n is 2 to 5, R ^{2 s} may be the same or different, and may combine with each other to form a ring.

It should be noted that when Y represents the atomic group necessary to complete the naphthalene nucleus, Ball and R ² can be attached to any of the ring systems so formed. IV Specific Configuration of the Invention Hereinafter, the specific configuration of the present invention will be described in detail.

The photothermographic material of the present invention has at least 3 different halogen compositions of adjacent layers in the silver halide grain.
It has at least one silver halide emulsion (multilayer structure emulsion) layer containing at least one type of photosensitive silver halide grains (multilayer structure silver halide grains) having a multilayer structure of at least one layer.

The average grain size of the above-mentioned multilayer structure type silver halide grains is 0.
The thickness is 1 to 5 μm, preferably 0.2 to 3 μm.

The composition of the whole grains of the multilayer structure type silver halide is
Although not particularly limited, silver bromide is mainly used, and the iodine content is preferably 20 mol% or less, more preferably 0 or more and 10 mol% or less in the total amount of halides present in the entire silver halide. It is preferable that the content of chlorobromide, iodobromide or chloroiodobromide is 60 mol% or less, particularly 0 or more and 50 mol% or less.

The silver halide emulsion in the present invention is preferably monodisperse.

The coefficient of variation is 25% or less, preferably 20% or less.

The halogen composition of each layer of the multilayer structure type silver halide grain is not particularly limited as long as the layers adjacent to each other are different, and the halogen composition of each layer is not limited to chlorine concentration or bromine concentration. The concentration may change. Alternatively, a combination of these (for example, chlorine concentration and bromine concentration) may be changed. Further, the halogen composition of each layer in the grain may be different, the outer layer and the inner layer sandwiching the intermediate layer may have the same halogen composition, and only the intermediate layer may have a different halogen composition.

Further, in order to change the halogen composition, halogen conversion may be performed using a halide having a higher solubility product for silver than that of the substrate. This halogen-converted layer may be the layer inside the grain or the outermost layer, or may be both the inner layer and the outermost layer.

In the present invention, the following multilayer structured emulsions are preferably used.

Halide content is substantially chlorine content 60 mol%
Hereinafter, a layer composed of chlorobromide or chloroiodobromide having an iodine content of 5 mol% or less and having a bromine content of 5 mol% or more, preferably 10 mol% or more different from that of the adjacent layer (may be higher or lower) Multilayered emulsion having at least one layer, halide content substantially 20% iodine content
At least one layer comprising the following iodobromide or chloroiodobromide and having an iodine content different from the adjacent layer by 3 mol% or more is used.
Multilayer structured emulsions having layers, and emulsions of the type (1), wherein each layer has a thickness of 100 Å or more, preferably 200 Å or more.

Also, in addition to this, JP-A-60-222844, 59-140444,
59-48755, 60-138538, 60-143331, 60-2
The multilayer structure type silver halide emulsions described in, for example, 54032 also give preferable results.

In the present invention, such a multi-layer structure emulsion is preferably used in a proportion of at least 40%, preferably 50% or more (in terms of silver weight ratio) of all silver halides in the same photosensitive layer.

The multilayer structure type emulsion has a clear layered structure inside the grain as described above, and the layered structure can be determined by an X-ray diffraction method, an XPS method, an EPMA method or the like.

An example of applying the X-ray diffraction method to silver halide grains is described in H. Hirsch, Journal of Photographic Science, Volume 10 (1962), pages 129 et seq. When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies the black condition (2d sin θ = nλ).

Regarding the measurement method of X-ray diffraction, Basic Analysis Chemistry Course 24 “X
Line analysis "(Kyoritsu Shuppan) and" Guide to X-ray diffraction "(Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as the target and use Kβ-ray of Cu as the source (tube voltage 40KV, tube current 60mA).
This is a method of obtaining the diffraction curve of the surface. To increase the resolution of the measuring instrument, the width of the slit (divergence slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer,
It is necessary to select the recording speed appropriately and confirm the measurement accuracy using a standard sample such as silicon.

When the emulsion grains have two or more distinct layered structures, a diffraction maximum due to the silver halide in the high bromine layer and a diffraction maximum due to the silver halide in the low bromine layer appear, and two or more peaks appear in the diffraction curve. However, this peak does not have to be a clear peak, and may be a shoulder-like peak.

In addition to X-ray diffraction method, XPS (X-ray Photo-electron Sp
ectro-seopy; X-ray photoelectron spectroscopy) can be used to determine the layered structure of emulsion grains.

In the XPS method, the chemical composition analysis of the surface of silver halide becomes possible by using the Kα _1,2 ray of Mg or the Kα _1,2 ray of Al as excitation light. In order to investigate the composition inside the particles, it is possible to combine the XPS method and etching means.

The definite layered structure having three or more layers in the present invention means a curve of the diffraction intensity of silver halide vs. the diffraction angle using Kβ rays of Cu in the diffraction angle (2θ) range of 38 ° to 42 °. When the emulsion is obtained, it preferably has two or more peaks and has a minimum portion between the peaks. However, it is not necessary that there are two or more distinct peaks as described above, and a shoulder-like peak may be used. In that case, the full width at half maximum of the peak becomes a value larger than Δ2θ = 0.25 °.

Even in the case of an emulsion in which two kinds of grains having different halogen compositions having no distinct layered structure coexist, two or more peaks or shoulders appear in the X-ray diffraction.

Such emulsions do not exhibit the excellent photographic performance obtainable with the present invention.

The silver halide emulsion is an emulsion of the invention, or 2
In addition to X-ray diffraction method, EPMA method (Electron-P
This is possible by using the robe Micro Analyzer method).

The EPMA method is to prepare a sample in which emulsion grains are well dispersed so that they do not come into contact with each other, irradiate with an electron beam, and perform elemental analysis of a very small portion by X-ray analysis by electron beam excitation. By this method, the characteristic X-ray intensities of silver and bromine emitted from each grain can be obtained, and the halogen composition of each grain can be determined.

The silver halide grain of the present invention has only to have a clear layer structure of three or more layers in the above meaning, and a transition layer of about 100 Å or less may exist between these layers.

The points to keep in mind when preparing a desirable multilayer structure type emulsion in the present invention are as follows.

i) The silver halide grains forming the innermost core are as uniform and monodisperse as possible, ii) The growth rate of the silver halide in the outer layer is 30 to 100% of the crystal critical growth rate for uniform coating. Addition at a relatively high degree of supersaturation, iii) The amount of silver in each layer within the grain is 1/1 of the total amount of silver in the grain.
00 to 1/2, iv) at least one layer in the grain may have a layer formed by halogen conversion, v) at least one layer in the grain is a layer aged with pAg7 or less. What it may have, vi) There is no particular restriction on the crystal habit, but normal crystals are preferable to twin crystals, and a cube having a Miller index (100) face on the outer surface and a (111) face on the outer surface It is good to comply with the conditions such as octahedron, and tetrahedron having both (100) and (111) faces.

In fact, at the stage of forming multi-layered type silver halide grains, Japanese Patent Publication No. 46-7781, Japanese Patent Application No. 59-79160, and Japanese Patent Laid-Open No. 60-1229.
Nitrogen-containing compounds such as those described in No. 35 can also be added.

It is possible to add a spectral sensitizing dye at the time of grain formation of the multilayer structure type emulsion of the present invention. The addition time may be before or after the nucleation or before or after the chemical sensitization. When added before nucleation, the particle size distribution broadens, it is desirable to add at the stage after core particle formation.

Emulsions are usually freed from soluble salts after precipitation or physical ripening. As a means for this purpose, the Nudel water washing method, which is a known method of gelling gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin) Sedimentation method (flocculation)
May be used. The process of removing soluble salts may be omitted.

For other conditions, see P.Glafki
des), Chimie et Physique Photographique [Paul
Published by Paul Montel, 1967), by GFDuffin, Photographic Emulsio Chemistry.
n Chemistry) [The Focal P
ress), 1966], by VL Zelikman et al, Making and Coating Photographic Emulsion (Making
and Coating Photographic Emulsion) [The Focal Press, 1964]. That is, any of an acidic method, a neutral method, and an ammonia method may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
It is also possible to use a method of keeping g constant, that is, a so-called controlled double jet method.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124 and US Pat. No. 3,650,757). etc).

During or after grain formation, the surface of the silver halide grain may be replaced with a halogen which forms a hardly soluble silver halide grain.

Further, the stirring method of the reaction solution may be any known stirring method. The concentration and pH of the reaction solution during the formation of silver halide grains
Can be set in any way.

In the step of forming the multi-layered type silver halide grains, as the silver halide solvent, rhodan salt, ammonia, JP-B-47
-11386 organic thioether derivatives or JP-A-53-53
The sulfur-containing compounds described in No. 144319 can be used.

Cadmium salt, zinc salt, lead salt, thallium salt and the like may be present together in the process of grain formation or physical ripening.

Furthermore, for the purpose of improving high-illuminance failure and low-illuminance failure, water-soluble iridium salts such as iridium chloride (III, IV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

The silver halide emulsion which can be used in combination with the emulsion of the present invention (mixed with the emulsion of the present invention and / or used in another layer of the same light-sensitive material) is silver chloride, silver bromide, or silver chlorobromide, silver chloroiodide, Either silver chloroiodobromide or silver iodobromide may be used.

Specifically, US Pat. No. 4,500,626, column 50, JP-A-5
8-108533, Research Disclosure, June 1978
Month issue, pages 9-10 (RD17029), JP-A-61-107240, JP-A-60-225176, 60-228267, 60-180199, 61-
Any of the silver halide emulsions described in 70056 etc. can be used.

Gelatin is advantageously used as the protective colloid used in the preparation of the multilayer structure type emulsion of the present invention and as the binder of other hydrophilic colloids, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, Various synthetic hydrophilic polymer substances such as single or copolymers such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole and the like can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, bulletin, and Society of the Scientific Photography of Japan (Bul
l.Soc.Sci.Phot.Japan), Sambar (No) 16, Pee (P) 30 (1966), oxygen-treated gelatin may be used, or a hydrolyzate or enzymatic decomposition of gelatin may be used. Objects can also be used.

Regarding photographic gelatin, "Basics of photographic engineering-silver salt photography", published on January 30, 1979, Corona 116
~ 150 pages, H. Amman, ed. “Restrains in Photographi
c Gelatain (1971) ”.

For the content of impurities in gelatin, see the former document 133.
~ See page 134.

As the photographic gelatin, lime-processed bone (ossein) gelatin is preferably used, and the content of impurities is particularly preferably within the above-mentioned range. For example,
The Ca content is preferably 0 to 6000 μg per 1 g of gelatin.

The multilayer structure type emulsion used in the present invention is chemically sensitized. For chemical sensitization, for example, H.Frieser Die Grundlagen der Photographishen P
rozesse mit Silderhalgeniden) [Akademische Verlagsges
ellschaft), 1968] p.675-734, the sulfur sensitization method, the reduction sensitization method, the selenium sensitization method, the noble metal sensitization method and the like can be used alone or in combination.

For example, in sulfur sensitization, sulfur sensitizers, that is, compounds containing sulfur obtained by reacting with active gelatin or silver include, for example, thiosulfates, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p -Toluenethiosulfonate, Rhodan, mercapto compounds and the like are used. Others, U.S. Pat.No. 1,574,944,
No. 2,410,689, No. 2,278,947, No. 2,728,668
Nos. 3,656,955 and the like can also be used.

The addition amount of these sulfur sensitizers varies over a considerable range under various conditions, but is usually preferably about 10 ^-7 to 10 ^-2 mol per mol of silver.

In gold sensitization, the gold sensitizer may have a gold oxidation number of +1 valence or +3 valence.
Potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid and the like are used.

The amount of these gold sensitizers added will vary over a considerable range under various conditions, but is usually 10 per mole of silver.
^It is preferably about ^-9 to 10 ^-2 mol.

In the present invention, selenium sensitizers can also be used, but selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters. , Selenophosphates, diethyl selenide, selenides such as dimethyl diselenide, and the like, and specific examples thereof are described in US Pat.
No. 574,944, No. 1,602,592, and No. 1,623,499.

The addition amount of the selenium sensitizer is selected from a wide range, but usually 10 ^-7 to 10 ^-2 mol per mol of silver is preferable.

In addition to the above-mentioned sulfur sensitization, gold sensitization and selenium sensitization, a reduction sensitization method using a reducing substance (eg, primary tin salt, amines, hydrazine derivative, formamidinesulfinic acid, silane compound); noble metal compound (For example, besides gold complex salt
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, and Pd) can also be used in combination.

Regarding the reduction sensitization method, U.S. Patent Nos. 2,983,609 and
No. 2,419,974, No. 4,054,458 and the like, and the noble metal sensitization method are described in US Pat. Nos. 2,399,083, 2,448,060 and British Patent 618,061.

Typical combinations of sensitizers are gold / sulfur sensitization and gold / selenium sensitization, but other combinations are also possible. In gold / sulfur sensitization, the use ratio of both sensitizers varies depending on the aging conditions and the like, but usually 1 to 1000 mol of the sulfur sensitizer is used per 1 mol of the gold sensitizer.

For gold / selenium sensitization, it is usually preferable to use about 1 to 1000 mol of the selenium sensitizer per mol of the gold sensitizer.

In gold / sulfur sensitization or gold / selenium sensitization, the gold sensitizer may be added at the same time as the sulfur sensitizer or the selenium sensitizer, or during or after the sulfur or selenium sensitization.

Particularly preferred chemical sensitization for use in the present invention is sulfur sensitization or gold-sulfur sensitization.

In the present invention, these chemical sensitizers are added to the silver halide photographic emulsion by a conventional method. That is, the water-soluble compound is added as an aqueous solution, and the compound soluble in an organic solvent is added as a solution of an organic solvent that is easily mixed with water, such as methanol or ethanol.

The conditions such as pH, pAg and temperature during chemical sensitization are not particularly limited, but the pH value is preferably 4-9, especially 5-8, and the pAg value is kept at 5-11, especially 7-10. Is preferred. Further, the temperature is preferably from 40 to 90 ° C, particularly preferably from 45 to 75 ° C.

Further, it is well known in the art that these chemical sensitizations are carried out in the presence of a nitrogen-containing heterocyclic compound (British Patent No. 1315755, JP-A-50-63914, JP-A-51-77223).
No. 58-126526 and 58-215644).

Chemical sensitization in the presence of an acetylene compound as described in JP-B-39-22067 and 39-22068 is also useful for obtaining a silver halide emulsion having a low fog.

When a light-sensitive material is formed using the emulsion of the present invention, it is possible to mix different emulsions to form a color-sensitive layer, or different emulsions having the same color-sensitivity are coated in different layers. It is also possible to form the light-sensitive material with the same color-sensitive layer having a multi-layer structure.

The object of the present invention can be achieved by using at least one of the compounds represented by the following general formula (I) or (II) in combination with the above-mentioned multi-layer structure type silver halide emulsion.

General formula (I) General formula (II) In the above general formulas (I) and (II), R ¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group.

Examples of the above-mentioned preferred R ¹ include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group, dodecyl group and the like; substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, For example, cyclohexyl group and the like; substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, such as benzyl group, β-phenethyl group and the like; substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl group and naphthyl group, Tolyl group, xylyl group, etc .; substituted or unsubstituted amino group having 0 to 30 carbon atoms, for example, amino group, methylamino group, isopropylamino group, cyclohexylamino group, phenylamino group, benzylamino group, N, N-dimethyl Amino group, N-methyl-N-ethylamino group, N, N
-Diisopropylamino group, N, N-dicyclohexylamino group, N, N-diphenylamino group, N, N-dibenzylamino group; substituted or unsubstituted heterocyclic group such as pyridyl group, furyl group, thienyl group Can be mentioned.

Further, when the substituent of the aryl group is described in detail, examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an amino group, an alkoxy group, an aryloxy group, a hydroxyl group, an aryl group, a carbonamido group, an alkanoyl group. Oxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group,
Examples thereof include a carboxy group, an alkyl group (methyl group, ethyl group, propyl group, etc.), an acylamino group, a sulfamoyl group, an ester group, an alkylsulfonyl group, an alkylsulfonylamino group, and an arylsulfonylamino group.

R ² is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group. Represents a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group or an arylthio group.

As a preferred example of R ² , a hydrogen atom; a halogen atom,
For example, a bromine atom, a chlorine atom, etc .; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group,
Isopropyl group, t-butyl group and the like; substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, such as cyclopentyl group, cyclohexyl group and the like; substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, such as benzyl group, β-phenethyl group and the like; substituted or unsubstituted aryl group having 6 to 20 carbon atoms, such as those mentioned in the item of R ¹ such as phenyl group, naphthyl group and the like; substituted or unsubstituted heterocyclic group, for example pyridyl group, Furyl group, thienyl group, etc .; substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, such as methoxy group, butoxy group, methoxyethoxy group; 6 to 20 carbon atoms
A substituted or unsubstituted aryloxy group, such as a phenoxy group; a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, such as an acetyl group or palmitoyl group;
20 substituted or unsubstituted alkyloxycarbonyl groups such as methoxycarbonyl group; aryloxycarbonyl groups having 6 to 20 carbon atoms such as phenoxycarbonyl group; substituted or unsubstituted carbamoyl groups having 1 to 20 carbon atoms, such as , A methylcarbamoyl group, a dimethylcarbamoyl group, a diisopropylcarbamoyl group, etc .; a substituted or unsubstituted sulfamoyl group having 1 to 20 carbon atoms, such as a dimethylsulfamoyl group; a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms , For example, a methylsulfonyl group and the like; a substituted or unsubstituted arylsulfonyl group having 6 to 20 carbon atoms, for example, a phenylsulfonyl group, p
-Methylphenylsulfonyl group, etc .; Substituted or unsubstituted acylamino group having 2 to 20 carbon atoms, such as acetylamino group, N-methylacetylamino group, palmitoylamino group, etc .; Substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms Examples thereof include groups such as methylthio group and ethylthio group; and substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as phenylthio group and m-methoxycarbonylphenylthio group.

n represents an integer of 0 to 5, and when n is 2 to 5, R ^{2 s} may be the same or different, and may combine with each other to form a ring.

Examples of such a ring include bicyclo [2.2.1] hept-2-fused with a benzene ring completed by Y described later.
Examples thereof include ene and cyclohexene.

Ball represents a ballast group capable of rendering the compounds represented by these formulas non-diffusible.

However, when R ¹ is a non-diffusible group, Ball may not be present.

The nature of the ballast group (Ball) is not critical as long as the ballast imparts diffusion resistance to this compound. Common ballast groups are straight or branched straight chain alkyl groups that are directly or indirectly attached to the compound, and are either indirectly attached to or directly attached to the benzene nucleus. Benzene-based and naphthalene-based aromatic groups are included. Effective ballast groups are generally groups having at least 8 carbon atoms, substituted or unsubstituted alkyl groups having 8 to 30 carbon atoms, acylamino groups having 8 to 30 carbon atoms,
Acyl group having 8 to 30 carbon atoms, acyloxy group having 8 to 30 carbon atoms, alkoxy group having 8 to 22 carbon atoms, alkylthio group having 8 to 30 carbon atoms, 8 to 30 carbon atoms 8 carbon atoms having an alkoxycarbonyl group
To any of 30 alkoxy groups. Also,
As an example of indirectly bonding, a carbamoyl group or a sulfamoyl group represented by the following general formulas (A) and (B) (the nitrogen atom contained in these groups is bonded to a ballast group) is bonded. It is a thing.

In the above formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (eg methyl group, ethyl group etc.), a cycloalkyl group (eg cyclohexyl group etc.) or an aryl group (eg phenyl group etc.).

L is a divalent group (eg, alkylene group, phenylene group, 2
A valent arylthio group), and m represents 0 or 1.

Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus.

It should be noted that when Y represents the atomic group necessary to complete the naphthalene nucleus, Ball and R ² can be attached to any of the ring systems so formed.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the compounds of the present invention are not limited thereto.

The compounds of the present invention may be used alone or in combination of two or more.

It may be contained in any layer of the light-sensitive material such as an emulsion layer, an intermediate layer and a protective layer, but it is particularly effective to add it to a dispersion of a dye-providing substance and to add it to the emulsion layer. .

The addition amount is 0.0005 to 20 times mol, and particularly useful addition amount range is 0.001 to 4 times mol to silver.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulfinic acid, benzenesulphonic acid amide and the like can be added. For example, U.S. Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication Sho
Those described in No. 52-28660 and the like can be used.
Further, the acetylene compounds described in JP-B Nos. 39-22067 and 39-22068 are also useful as antifoggants. For more specific examples of acetylene compounds, reference can be made to JP-A No. 61-72233. The following compounds are specific examples of the antifoggant.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for example, polyalkylene oxide or an ether, ester thereof,
Derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like may be included. For example, U.S. Patent No. 2,400,532
No. 2,423,549, No. 2,716,062, No. 3,617,28
No. 0, No. 3,772,021, No. 3,808,003, British Patent No.
What was described in 1,488,991 can be used.
The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. It is also possible to use a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined. Internal latent image type emulsions suitable for this purpose are described in US Pat. Nos. 2,592,250, 3,761,276, JP-B-58-3534 and JP-A-57-136641. Preferred nucleating agents to be combined in the present invention are described in U.S. Pat.

The silver halide used in the present invention is a methine dye,
It may be spectrally sensitized by other means. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazole nucleus,
Selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nuclei, benz Indolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, or a thiobarbitutumate nucleus can be applied.

Specifically, JP-A-59-180550 and JP-A-60-140335, Research Disclosure June 1978, pages 12 to 13 (RD-17029), and U.S. Pat. Nos. 1,846,300 and 2,0
78,233, 2,089,129, 2,165,338, 2,
No. 231,658, No. 2,917,516, No. 3,352,857, No. 3
No. 3,411,916, No. 2,295,276, No. 2,481,698, No. 2,688,545, No. 2,921,067, No. 3,282,933,
No. 3,397,060, No. 3,660,103, No. 3,335,010
No. 3,352,680, No. 3,384,486, No. 3,623,88
1, No. 3,718,470, and No. 4,025,349.

The heat-decolorizing dye is described in JP-A-60-111239, Japanese Patent Application No. 60-172967, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization (US Pat. No. 3,506,
No. 443, No. 3,672,898, etc.).

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminomistyl compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, described in US Pat. No. 3,743,510) ), Cadmium salt, azaindene compound and the like. U.S. Pat.Nos. 3,615,613, 3,615,641 and 3,617,29
The combinations described in No. 5 and No. 3,635,721 are particularly useful.

To incorporate these sensitizing dyes in a silver halide photographic emulsion, they may be dispersed directly in the emulsion, or they may be used alone or in a solvent such as water, methanol, ethanol, acetone or methyl cellosolve. It may be dissolved in a mixed solvent and added to the emulsion. Alternatively, they may be dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid, and this dispersion may be added to the emulsion.

Further, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. When these sensitizing dyes are dissolved, the sensitizing dyes used in combination may be dissolved separately, or a mixture thereof may be dissolved. Also, when they are added to the emulsion, they may be added simultaneously as a mixture, separately, or simultaneously with other additives. The time of addition to the emulsion may be before or after chemical ripening, or before or after nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. When the sensitizing dye is added to the emulsion, the pH of the emulsion is preferably 3-11.

The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

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 silver salt, which is relatively stable to light, can be used as an oxidizing agent together with the photosensitive silver halide. In this case, it is necessary that the photosensitive silver halide and the organic silver salt are in contact with each other or in a close distance.

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

Such an organic metal salt is effective when the photothermographic material is heated to a temperature of 50 ° C. or higher, preferably 60 ° C. or higher for development.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids,
Examples thereof include thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds.

Examples of the silver salt of an aliphatic carboxylic acid include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, linolenic acid, adipic acid. Typical examples are silver salts derived from sebacic acid, succinic acid, acetic acid, butyric acid, propiolic acid or camphoric acid. A silver salt derived from a halogen atom or hydrogen substitution product of these fatty acids, or an aliphatic carboxylic acid having a thioether group can also be used.

The silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoic acid, 3,5-dihydroxybenzoic acid, o-, m- or p-methylbenzoic acid, 2,
4-dichlorobenzoic acid, acetamidebenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl-4-thiazoline A typical example is a silver salt derived from 2-thione or the like. The silver salt of a compound having a mercapto or thiocarbonyl group is 3-mercapto-4-
Phenyl-1,2,4-toluazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2-mercaptobenzothiazole, S-alkylthioglycolic acid (alkyl group having 12 to 2 carbon atoms)
2), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearoamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3 Examples thereof include silver salts derived from mercapto compounds described in US Pat. No. 4,123,274, such as -amino-5-benzylthio-1,2,4-triazole.

As a silver salt of a compound having an imino group, Japanese Patent Publication No. 44-3
No. 0270 or No. 45-18416, or benzotriazole or a derivative thereof, for example, alkyl-substituted benzotriazoles such as benzotriazole and methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole, and carboximidobenzo such as butylcarbimidetriazole. Triazoles, JP-A-58-1
Nitrobenzotriazoles described in 18639, JP-A-58-
118638 described sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole, such as 1,2,4-triazole or 1H-tetrazole, carbazole, saccharin, imidazole and derivatives thereof described in U.S. Pat. Representative examples are derived silver salts.

Further, organic metal salts other than silver salts such as silver salts and copper stearate described in RD17029 (June 1978), JP-A-60,
A silver salt of a carboxylic acid having an alkyl group such as phenylpropiolic acid described in No. 113235 can also be used in the present invention.

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 the present invention, silver can be used as the image forming substance. Also, when a photosensitive silver halide is reduced to silver under high temperature conditions, it contains a compound that produces or releases a mobile dye in response to this reaction or vice versa, that is, contains a dye-donor substance. You can also do it.

 Next, the dye-providing substance will be described.

As an example of the dye-donating substance that can be used in the present invention, first, a coupler capable of reacting with a developing agent can be mentioned. The method using a coupler is a method in which an oxidized form of a developing agent generated by an oxidation-reduction reaction between a silver salt and a developing agent reacts with the coupler to form a dye, and is described in many documents. Specific examples of developing agents and couplers can be found in "The Theory of the Photographic Process," 4th edition, by James (TH James "The Theory o
f the Photographic Process ") pages 291-334, and 354
Pages-361, JP-A-58-123533, JP-A-58-149046, JP-A-58-123533
149047, 59-111148, 59-124339, 59-17483
No. 5, No. 59-231539, No. 59-231540, No. 60-2950, No.
60-2951, 60-14242, 60-23474, 60-66249
No. is described in detail.

Further, a dye silver compound in which an organic silver salt and a dye are bound can also be mentioned as an example of the dye donating substance. Specific examples of dye silver compounds are described in Research Disclosure, May 1978, pp. 54-58 (RD-16966).

Further, an azo dye used in the heat developable silver dye bleaching method can also be mentioned as an example of the dye-donating substance. Specific examples of azo dyes and bleaching methods are described in US Pat. No. 4,235,957, Research Disclosure, April 1976, pages 30 to 32 (RD-14433) and the like.

Further, leuco dyes described in U.S. Pat. Nos. 3,985,565 and 4,022,617 can be cited as examples of dye-donor substances.

As another example of the dye-donating substance, a compound having a function of releasing or diffusing a diffusible dye in an image form can be mentioned.

This type of compound can be represented by the following general formula [LI].

(Dye-X) n-Y [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or linking group, and Y represents an image-wise latent image. Corresponding to or opposite to the photosensitive silver salt having (Dye-X) n-Y, or causing a difference in diffusivity of the compound represented by (Dye-X) n-Y. X) n-Y represents a group having a property of causing a difference in diffusibility, and n represents 1 or 2, and when n is 2, two Dye-X are the same or different. Good.

Specific examples of the dye-providing substance represented by the general formula (LI) include, for example, a dye developing agent in which a hydroquinone-based developing agent and a dye component are linked, U.S. Patent Nos. 3,134,764 and
3,362,819, 3,597,200, 3,544,545, 3,482,972 and the like. Further, a substance which releases a diffusible dye by an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51
-63,618 and the like, a substance which releases a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring is disclosed in JP-A-49-1.
It is described in No. 11,628. In all of these methods, the diffusible dye is released or diffused in a portion where development has not occurred, and the dye is neither released nor diffused where development has occurred.

Another method is to make a dye-releasing compound coexist with a reducing agent or its precursor even if it is an oxidant type that does not have a dye-releasing ability, and after development, it is reduced by the reducing agent remaining unoxidized and diffusible. A method of releasing a dye has also been devised, and specific examples of the dye-donor substance used therein are disclosed in JP-A Nos. 53-110,827, 54-130,927, 56-164,342, and
No. 53-35533.

On the other hand, as a substance that releases a diffusible dye at a portion where development has occurred, a substance that releases a diffusible dye by a reaction between a coupler having a diffusible dye as a leaving group and an oxidant of a developer is British Patent 1,330,524. And Japanese Patent Publication No. 48-39,165, and U.S. Pat. No. 3,443,940.

In addition, in the system using these color developing agents, the contamination of the image by the oxidative decomposition product of the developing agents becomes a serious problem, so for the purpose of improving this problem, the developing agents are not necessary and the reducing property itself is reduced. Dye-releasing compounds that have been devised.

Typical examples thereof are, for example, U.S. Pat.Nos. 3,928,312, 4,053,312, 4,055,428, and 4,336,322,
JP-A-59-65839, 59-69839, 53-3819, 51-
104343, Research Disclosure 17465,
U.S. Pat.Nos. 3,725,062, 3,728,113, 3,443,
It is a dye-donor substance described in 939, JP-A-58-116,537, 57-179840, US Pat. No. 4,500,626 and the like.

Specific examples of the dye-donating substance that can be used in the present invention include:
The compounds described in columns 22 to 44 of the above-mentioned U.S. Pat. No. 4,500,626 can be mentioned. Among them, the compounds (1) to (3) and (10) to (13) described in the above-mentioned U.S. Pat. ,
(16) ~ (19), (28) ~ (30), (33), (35),
(38) to (40) and (42) to (64) are preferred. Further, the compounds described in JP-A No. 61-124941 are also useful.

The above-mentioned dye-providing compounds and hydrophobic additives such as image forming accelerators described below can be incorporated into the layers of the light-sensitive material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-
No. 178454, No. 59-178455, No. 59-178457, etc., a high boiling point organic solvent, if necessary, boiling point 50 ℃ ~ 160
It can be used in combination with an organic solvent having a low boiling point of ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, with respect to 1 g of the dye-donor substance used.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

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. Further, when dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used, and those surfactants are disclosed in JP-A-59-157636 (37) to (3).
8) The surfactants listed on page 8 can be used.

In the present invention, the light-sensitive material contains a reducing substance. Examples of the reducing substance include those generally known as a reducing agent, and the dye-donating substance having the above-described reducing property. Also included are reducing agent precursors which do not themselves have a reducing property but exhibit a reducing property by the action of a nucleophile or heat during the development process.

Examples of reducing agents used in the present invention include US Pat.
4,500,626, columns 49-50, 4,483,914, columns 30-31
Column, pages (17) to (18) of JP-A-60-140335, JP-A-6-
0-128438, 60-128436, 60-128439, 60-128
The reducing agents described in No. 437, etc. can be used. In addition, JP-A-56-
The reducing agent precursors described in 138736, 57-40245, US Pat. No. 4,330,617 and the like can also be used.

Combinations of various developers such as those disclosed in US Pat. No. 3,039,869 can also be used.

In the present invention, the reducing agent is added in an amount of 1 mol of silver.
It is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, an image formation accelerator can be used in the light-sensitive 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 mobile 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.

Details of these are described in JP-A-61-93451.

There are various methods of generating a base in addition to the above-mentioned image formation accelerator, and all the compounds used in the method are useful as a base precursor. For example, Japanese Patent Application Sho 60-169
No. 585, a method for generating a base by mixing a sparingly soluble metal compound and a compound capable of complexing with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound) described in Japanese Patent No. 585 There is a method of generating a base by electrolysis described in No. 74702.

The former method is particularly effective. Examples of the hardly soluble metal compound include carbonates such as zinc, aluminum, calcium and barium, hydroxides and oxides. Further, regarding the complex forming compound, for example, A.E.
Co-authored by AEMartell, RMSmith, "Critical Stability Constants (Cr
itical Stabillity Constants) ", Volumes 4 and 5,
It is described in detail in Plenum Press.
Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and further phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino A compound having a substituent such as), an alkali metal such as hydroxamic acids, polyacrylates and polyphosphoric acids, and a salt with guanidines, amidines, quaternary ammonium salts and the like.

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 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 thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (eg, JP-A- 60-108837, 60-192939, 60
-230133 or the compounds described in 60-230134).

Further, a compound which releases a mercapto compound by heating is also useful, for example, JP-A Nos. 61-67851 and 61-147244.
No. 61, No. 61-124941, No. 61-185743, No. 61-182039,
61-185744, 61-184539, 61-188540, 61-
There are compounds described in 53632.

Further, in the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material.

Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

Various antifoggants can be used in the present invention. Antifoggants include azoles and JP
Nitrogen-containing carboxylic acids and phosphoric acids described in 59-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in Japanese Patent Application No. 60-228267 are used. To be

In the present invention, the light-sensitive material may optionally contain an image toning agent. Specific examples of effective toning agents include the compounds described in JP-A-61-147244.

The binder used in the light-sensitive material of the present invention may be contained alone or in combination. As the binder, a hydrophilic binder can be used. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include proteins such as gelatin and gelatin derivatives, natural substances such as polysaccharides such as cellulose derivatives, starch and gum arabic, and polyvinylpyrrolidone. , Synthetic polymer materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latex, in particular for increasing the dimensional stability of the photographic material.

In the present invention, the binder is applied in an amount of 20 g or less per 1 m ² , preferably 10 g or less, more preferably 7 g.
The following are appropriate:

The ratio of the high boiling point organic solvent and the binder dispersed together with the hydrophobic compound such as the dye-providing substance in the binder is 1 cc or less of the solvent per 1 g of the binder, preferably 0.5 cc or less, and more preferably 0.3 cc or less. is there.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other binder layers.

Specific examples of the hardener are disclosed in JP-A-61-147244 and JP-A-59-15.
No. 7636, page (38) can be mentioned, and these can be used alone or in combination.

The support used for the light-sensitive material and optionally the dye-fixing material of the present invention can withstand the processing temperature. As a general support,
In addition to glass, paper, polymer films, metals and analogs thereof, those listed as supports in JP-A-61-147244 can be used.

Further, filter dyes, absorbent substances, and the like described in the documents exemplified in JP-A-61-147244 and U.S. Pat. No. 4,500,626 at column 55 (lines 41 to 52) can be incorporated.

Even when the dye-donating substance is colored yellow, magenta or cyan, the sharpness can be further improved by providing the antihalation layer. Especially when the light-sensitive material has an infrared-sensitive layer, the antihalation layer is essential.

The antihalation layer may be formed using a known dye or pigment. In order to provide the antihalation layer on the infrared photosensitive layer, it is advantageous to use an infrared absorber or carbon black. It is particularly advantageous to use carbon black, the base may be colored or the carbon black-containing layer may be provided separately. As a specific embodiment, the one described in Japanese Patent Application No. 61-18963 can be used.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, the light-sensitive material of the present invention comprises at least three silver halide emulsion layers each having light-sensitivity in different spectral regions. Need to have.

A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in JP-A-59-180550.

The light-sensitive material of the present invention may optionally have two or more emulsion layers having photosensitivity in the same spectral region depending on the sensitivity of the emulsion.

The photosensitive material in the present invention, if necessary, various additives known as photothermographic materials and layers other than the photosensitive layer, for example, an antistatic layer, a conductive layer, a protective layer, an intermediate layer, AH.
Layers, release layers, matte layers and the like can be included. As various additives, Research Disclosure Magazine Vol.
170, an additive described in No. 17029 of June 1978,
For example, plasticizer, sharpness improving dye, AH dye, sensitizing dye,
There are additives such as matting agents, surfactants, optical brighteners, ultraviolet absorbers, slip agents, antioxidants and anti-fading agents.

In particular, the protective layer (PC) usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant, a UV absorber and the like. The protective layer and the intermediate layer may each be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent for preventing color mixture, a UV absorber, and a white pigment such as TiO ₂ . The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of increasing the sensitivity.

The photographic element of the present invention is composed of a light-sensitive element that forms or releases a dye by heat development and, if necessary, a dye-fixing element that fixes the dye.

Particularly, in a system for forming an image by diffusion transfer of a dye, a light-sensitive element and a dye-fixing element are essential, and as a typical form, the light-sensitive element and the dye-fixing element are separately coated on two supports. The form is roughly divided into a form coated on the same support.

Regarding the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in JP-A-61-147244 and U.S. Pat. No. 4,500,626, column 57 can be applied to the present application. .

A typical form in which the light-sensitive element and the dye-fixing element are coated on the same support is one in which it is not necessary to peel the light-sensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred forms include, for example, transparent support / photosensitive layer / white reflective layer / dye fixing layer, transparent support / dye fixing layer / white reflecting layer / photosensitive layer, and the like.

Other typical forms in which the light-sensitive element and the dye-fixing element are coated on the same support are described, for example, in JP-A-56-67840, Canadian Patent 674,082, and U.S. Patent No. 3,730,718. As described above, there is a mode in which a part or the whole of the light-sensitive element is peeled off from the dye fixing element, and a peeling layer is coated at an appropriate position.

The light-sensitive element or the dye-fixing element may be in a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of a dye.

In this case, the transparent or opaque heating element can be made using a conventionally known technique as a resistance heating element.

As the resistance heating element, there are a method of using a thin film of an inorganic material showing a semiconductor and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. As materials that can be used in these methods, those described in Japanese Patent Application No. 59-151815 can be used.

The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Regarding the layer structure of the dye fixing element, the binder, the additive, and the installation position of the mordant addition layer, those described in JP-A-61-147244 and the patent specifications cited therein can be applied to the present application.

The dye fixing element used in the present invention may be provided with an auxiliary layer such as a peeling layer, a matting agent layer and an anti-curl layer in addition to the above layers.

In one or more of the above layers, a base and / or base precursor for promoting dye transfer, a hydrophilic thermal solvent, an anti-fading agent for preventing discoloration of the dye, a UV absorber, a slip agent, and a matte. Agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, optical brighteners and the like may be included. Specific examples of these additives are disclosed in JP-A-61-882.
No. 56.

The binder in the above layer is preferably hydrophilic, and is typically a transparent or semitransparent hydrophilic colloid. Specifically, the binders listed above for the photosensitive material are used.

The image receiving layer in the present invention includes a dye fixing layer used in a heat-developable color light-sensitive material, and can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic portion, a polymer having a quaternary cation group thereof, or the like.

Specific examples thereof are described in JP-A-61-147244 and U.S. Pat. No. 4,500,626, columns 57-60.

In the present invention, the photothermographic layer, the protective layer, the intermediate layer, the undercoat layer, the coating method of the back layer and other layers are US Pat.
The method described in Columns 55 to 56 of No. 626 can be applied.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used, for example, in JP-A-61-147244 and U.S. Pat. The described light sources can be used.

The heating temperature in the heat development step can be developed at about 50 ° C to about 250 ° C, but particularly about 80 ° C to about 180 ° C is useful, and the heating temperature in the transfer step is different from the temperature in the heat development step. Transfer is possible in the range of room temperature, but it is particularly preferable that the temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. As a heating means in the developing and / or transferring step, a heating plate, an iron, a heating roller, a heating element using carbon, titanium white or the like can be used.

Further, as described in detail in JP-A-59-218443 and Japanese Patent Application No. 60-79709, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent such as water. Is also useful. In this method, the above-mentioned image forming accelerator may be contained in advance in either or both of the dye fixing material and the photosensitive material, or may be supplied from the outside.

In the system in which the development and the transfer are performed simultaneously or continuously, the heating temperature is preferably 50 ° 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.

In addition, a solvent may be used to move the movable dye to the dye fixing layer.

Examples of the solvent used for accelerating the development and / or moving the movable 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 is used). 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 in the method of applying to the dye fixing material or the light-sensitive 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). The specific amount is preferably ^{2 to} 35 g / m ² , and more preferably 3 to 25 g / m ² .

The solvent (for example, water) accelerates image formation and / or dye transfer by being applied between the photosensitive layer of the photothermographic material and the dye-fixing layer of the dye-fixing material. It can also be used by being incorporated in the dye fixing layer or both.

As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, there is a method described in JP-A-61-147244.

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, alcohols,
There are oximes and other heterocyclic groups.

The heating means in the transfer step is described in JP-A-61-147244. Alternatively, a layer of a conductive material such as graphite, carbon black or metal may be superposed on the dye fixing material, and an electric current may be passed through the conductive layer to directly heat the conductive layer.

JP-A-61-147 discloses a method for applying a pressure condition and a pressure when the heat-developable light-sensitive material and the dye-fixing material are superposed and brought into close contact with each other.
The method described in No. 244 can be applied.

According to the present invention, (i) high sensitivity and maximum image density (Dma
x) is high and fog (Dmin) is low, (ii) there is less sensation of increase / decrease due to pressure compared to a uniform halogen distribution emulsion in grains, (iii) sensitivity change due to temperature and humidity fluctuations during exposure. It is possible to obtain a photothermographic material having the following characteristics: (1) less latent image, (4) less latent image regression and good raw storability.

VI Specific Examples of the Invention Hereinafter, the present invention will be described in more detail by showing specific examples of the invention.

Example 1 A method for preparing a gelatin dispersion of a cyan dye-donor substance containing the compound of the present invention will be described.

5 g of cyan dye-donating substance (E), 0.2 g of compound (2) described in the text of the specification, 0.2 g of antifoggant (C), and succinic acid-2-ethyl-hexyl ester sulfonic acid as a surfactant 0.5 g of soda and 10 g of triisononyl phosphate were weighed, 30 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 100 g of a 3% solution of lime-processed gelatin were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as Dispersion 1 of cyan dye-donor material.

A dispersion obtained by removing the above compound (2) from the above dispersion 1 was prepared as a dispersion 2 of a cyan dye-donating substance for comparison and control. In addition, Dispersion 3 was prepared in the same manner except that Comparative Compound (X) was used instead of Compound (2) in Dispersion 1.
Was prepared.

Multilayer structure emulsion of the present invention and core / comparative for comparison
Described below is how to make shell type and uniform type emulsions.

Well-mixed lime-processed bone gelatin (Ca content 2500 pp
m) Aqueous solution (gelatin 20g and sodium chloride 2 in 800ml water)
g and compound 0.015 g was dissolved and kept at 50 ° C.), the following solutions I and II were simultaneously added, and solution I was added over 12 minutes and solution II over 8 minutes. 16 minutes after the addition of the solution I is added to the solution IV over a period of 44 minutes, and 20 minutes after the addition of the solution I is added to the solution III.
Added over minutes. The pAg from the end of the addition of solution I to the start of the addition of solution III was 6.7.

In addition, lime-processed bone gelatin (Ca content
2500ppm) aqueous solution (gelatin 20g and sodium chloride 4g and compound in 800ml water) 0.015 g was dissolved and kept at 45 ° C.), and the following solutions I and II were added over 20 minutes. After leaving it for 10 minutes,
Solution III and solution IV were added over 15 minutes. After standing for another 10 minutes, Solution V and Solution VI were added over 10 minutes.

Emulsions 1-8 were washed with water, desalted, and then lime-treated bone gelatin (Ca
The content was adjusted to pH 6.0 and pAg 7.7 by adding 25 g (content of 4000 ppm) and 100 ml of water. Then, optimal chemical sensitization was carried out at 55 ° C. using 1.1 mg of triethylthiourea and 60 mg of 4-hydroxy6-methyl-1,3,3a, 7-tetrazaindene. The yield of emulsion is
It was 650 g. Also, the emulsions 1 to 8 obtained have a grain size.
The particles were cubic monodisperse particles with a coefficient of variation of 0.35μ and 9 to 17%.

When examined by X-ray diffraction, XPS method, and EPMA method, it was confirmed that Emulsions 1 to 6 were the multilayer structure type grains of the present invention.

The method for preparing the organic silver salts (1) and (2) will be described.

Organic Silver Salt (1) A method for preparing a benzotriazole silver emulsion will be described.

28 g of lime-treated bone gelatin (seri strength 250 g) and 13.2 g of benzotriazole were dissolved in 300 ml of water. Add this solution to 40
The mixture was kept at ℃ and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then adjust the pH to 6.30,
A yield of 400 g of benzotriazole silver emulsion was obtained.

Organic silver salt (2) 20 g of lime-treated cowhide gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of 0.1% sodium hydroxide aqueous solution and 200 ml of ethanol.

 The solution was kept at 40 ° C. and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes.

The pH of this dispersion was adjusted and allowed to settle to remove excess salt. After that, the pH was adjusted to 6.3 to obtain a 300 g organic silver salt (2) dispersion.

Photosensitive materials 1 to 13 (Table 2) having the constitution shown in Table 1 were prepared using these dispersions and emulsions.

Next, how to make the dye fixing material will be described.

63 g of gelatin, 130 g of a mordant having the following structure and 80 g of potassium picolinate were dissolved in 1300 ml of water, and coated on a paper support laminated with polyethylene so as to have a wet film thickness of 45 μm, and then dried.

Further, a solution prepared by dissolving 35 g of gelatin and 1.85 g of 1,2-bis (vinylsulfonylacetamidoethane) in 800 ml of water was coated and dried to a wet film thickness of 17 μm to prepare a dye fixing material.

1/10 at 2000 lux through the neutral gray wedges whose densities are continuously changing
Exposure was for 0 seconds.

7 ml / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the layers were superposed so that the dye fixing material and the film surface were in contact with each other.

Using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was 90 ° C., it was heated for 25 seconds.

Then, when the dye fixing material was peeled off, a clear image of cyan was obtained on the fixing material.

Table 2 shows the minimum density (Dmin), maximum density (Dmax) and relative sensitivity of each light-sensitive material. The sensitivity was examined at the minimum density (Dmin) +0.3, and the sensitivity of the photosensitive material 9 was determined as 100.

As is clear from Table 2, the light-sensitive material of the present invention (combination of the multi-layer structure emulsion and the compound (2)) has low fog and high feeling.

Further, the pressure sensitizing properties of the light-sensitive materials 1, 3, 5 to 9 were examined. Each of the light-sensitive materials 1, 3, 5 to 9 was operated with a needle having a rounded tip and a constant load, and then developed to visually determine the degree of color development (pressure fog) in the unexposed area.

The photosensitive materials 1, 3, 5 to 8 of the present invention had less pressure fog than the comparative photosensitive material 9.

Environmental conditions for exposing photosensitive materials 1, 3, 5 to 10 are 15 ℃ -3
The exposure was changed to 0% RH, 25 ° C.-50% RH, 30 ° C.-70% RH, and the sensitivity variation due to the exposure environment was examined.

It has been found that the light-sensitive materials 1, 3, 5 to 8 of the present invention have extremely small changes in sensitivity due to the environment at the time of exposure as compared with the light-sensitive material 9 for comparison, and are superior to the light-sensitive material 10 for comparison. .

After the photosensitive materials 1, 3, 5 to 10 were allowed to stand at 40 ° C.-50% RH for 1 month and then subjected to sensitometry to examine the change in sensitivity and the change in Dmin, the photosensitive material of the present invention was compared with the comparative photosensitive material. There was little decrease in sensitivity and increase in Dmin.

When Compound AF-23 described in JP-A-60-198540 was used instead of Compound (2), Dmin = 0.53, Dm
Insufficient results were obtained with ax = 1.65 and relative sensitivity of 75.

Example 2 A method for preparing Emulsion 9 will be described.

Well-mixed lime-processed bone gelatin (ash content 0.4%,
Adenine content 0.2ppm) Aqueous solution (Gelatin 50g in 800ml water)
And 10 g of sodium chloride, 0.1 g of potassium bromide and 5 cc of sodium hydroxide (1N) are dissolved and kept at 60 ° C with AgN
An O ₃ aqueous solution (100 g of AgNO ₃ dissolved in water to make 600 ml in total) and an aqueous halide solution (54.5 g of KBr, 2 g of NaCl dissolved in water to make 600 ml in total) were simultaneously added all over 30 minutes. 1 minute after the end of addition, 0.2 g of sensitizing dye (A),
(B) A dye solution prepared by dissolving 0.2 g of water in 120 ml of water and 120 ml of methanol was added, and after 5 minutes, a 1% aqueous solution of potassium iodide.
10 ml was added.

After washing with water and desalting, lime-processed bone gelatin (adenine content 20
(ppm) 10 g and 50 ml of water were added to adjust the pH to 6.0 and pAg 7.6.

The obtained emulsion was kept at 60 ° C. and chemically ripened for 50 minutes using 2.5 mg of hypo. The yield of the emulsion was 600 g. This tetradecahedral monodisperse emulsion having an average size of 0.32 μ and a coefficient of variation of 11% is designated as Emulsion-9.

 Described below is how to make Emulsion-10.

Well-mixed gelatin aqueous solution (20g of lime-treated deionized bone gelatin (Ca content 20ppm) in 800ml of water, 4g of sodium chloride and 0.1g of potassium bromide) 0.015g and dissolved at 65 ° C) and silver nitrate aqueous solution (AgNO ₃ 50g dissolved in water to make 300ml in total)
And an aqueous halogen solution (KBr22.8g, NaCl6g dissolved in water to make the whole 300ml) were simultaneously added over 30 minutes. Next, the temperature of the solution was lowered to 35 ° C, and an aqueous solution of silver nitrate (50 g of AgNO ₃ dissolved in water to make a total of 300 ml) and an aqueous solution of halide (KBr31.5 g, NaCl.7 g dissolved in water to a total volume of 300 ml) were added. ) Was added simultaneously over 30 minutes.

After washing with water and desalting, lime-processed bone gelatin (guanine content 50
(ppm) 25 g and 100 ml of water were added to adjust the pH to 6.3 and pAg to 7 g.

The resulting emulsion was kept at 55 ° C and triethylthiourea 0.8m
Optimum chemical sensitization was carried out using 100 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. The yield of emulsion was 650 g. This cubic monodisperse emulsion having an average size of 0.5 μ and a coefficient of variation of 9% is designated as Emulsion-10.

 Described below is how to make Emulsion-11.

Well-mixed lime-treated bone gelatin aqueous solution (800 m water)
20 g of gelatin, 4 g of sodium chloride and 0.
With 3g 0.015g dissolved in and kept at 45 ° C), silver nitrate aqueous solution (100g AgNO ₃ dissolved in water to make 600ml in total)
And an aqueous halide solution (56 g of KBr and 6.9 g of NaCl dissolved in water to make 600 ml in total) were simultaneously added over 60 minutes.

Further, the dye solution used in Emulsion-9 was added over 30 seconds to 20 minutes before the addition of the silver nitrate aqueous solution and the halogen aqueous solution.

After washing with water and desalting, 25 g of lime-treated deionized ossein gelatin (Ca content 300 ppm) and 100 ml of water were added to adjust pH to 6.1 and pAg to 7.9 g.

The obtained emulsion was kept at 60 ° C. and triethylthiourea
Optimal chemical sensitization was carried out using hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. Emulsion yield is 650g
Met. This cubic monodisperse emulsion having an average size of 0.28 μm and a coefficient of variation of 13% is designated as Emulsion-11.

A light-sensitive material having a multilayer structure as shown in Table 3 using these emulsions, dye-donor substances, organic silver salts (1) and organic silver salts (2).
101 to 104 were produced. The emulsions used are as follows.

The light-sensitive materials 101 to 104 obtained in this manner were subjected to G, R, and
It was exposed for 1/20 seconds at 2000 lux through an IR three color separation filter. 15 ml / m on the emulsion side of this exposed light-sensitive material
² of water was supplied by a wire bar, and then the same dye fixing material as that used in Example 1 was superposed so that the membrane surface was in contact.

Using a heat roller whose temperature was adjusted so that the temperature of the absorbed film was 90 ° C., it was heated for 25 seconds. Next, when the dye fixing material was peeled off, yellow, magenta and cyan images were obtained on the fixing material corresponding to the three color separation filters of B, G and R.

 The results obtained are summarized in Table 4.

From the results in Table 4, it can be seen that a highly sensitive light-sensitive material can be obtained by using the multilayer structure type emulsion of the present invention.

Also, when the short-time exposure for 10 ^-4 seconds was performed using a xenon flash tube, the light-sensitive material of the present invention had higher sensitivity as in the results shown in Table 4.

Next, the light-sensitive materials 101 to 104 are respectively placed at 10 ° C. and 30% relative humidity
Exposure was performed for 10 ⁻⁴ seconds using a xenon flash tube in an atmosphere of 35 ° C. and 70% relative humidity (through a three-color separation filter of G, R, and IR), and the same heating and development transfer processing were performed. Sensitivity difference between exposure sensitivity between 10 ° C 30% and 35 ° C 70%
1 to 104 were compared.

 Table 5 shows the results.

The values in the table are the sensitivity under the condition of 35 ℃ and 70%.
This is when the sensitivity under the condition of 30 ° C is set to 100.

As shown in Table 5, it is understood that the multilayer structure type emulsion has a small sensitivity variation due to the atmosphere during exposure.

Further, when the multilayer structure type emulsion of the present invention is used, when the amount of water supplied during the heat development processing is changed (in the above, 10 ml / m 2
² if you change the 20 ml / m ²⁾ was also found that the sensitivity change is small.

A scanning type exposure apparatus using the above light-sensitive materials 101 to 104 using three types of light emitting diodes of green, red and infrared rays (Japanese Patent Laid-Open No. 60-253284).
No. 1) was used to control the supply current to change the amount of light emission to provide image exposure.

Image exposure was carried out by changing the atmosphere using the above method, 13 ml / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material by a wire bar, and then the dye-fixing material and the film surface were superposed so that they were in contact with each other.

A heat roller whose temperature was adjusted so that the temperature of the absorbed film was 92 ° C was heated for 25 seconds. Next, when the dye fixing material was peeled off, yellow, magenta, and cyan images were obtained on the fixing material, corresponding to three types of light emitting diodes of green, red, and infrared.

Table 6 shows the densities of the respective exposure atmospheres at a current amount at which the densities of the respective colors of yellow, magenta, and cyan when exposed at 25 ° C. and 50% RH were 1.0.

It can be seen that the use of the multi-layer structure emulsion of the present invention requires less change in photographic performance even if the humidity during exposure changes.

In addition, in these Examples, the dye-donating compound itself has an action as a reducing agent.

Claims (1)

[Claims] 1. At least a silver halide emulsion on a support,
A photothermographic material having a reducing agent and a binder for a silver halide emulsion, wherein the silver halide emulsion has a multilayer structure of at least three layers in which adjacent layers have different halogen compositions in the silver halide grain. A compound containing at least one type of photosensitive silver halide grains and having at least one layer having such a silver halide emulsion and represented by the following general formula (I) or (II) A photothermographic material comprising at least one kind. General formula (I) General formula (II) {In the above general formulas (I) and (II), Ball is an organic ballast group capable of rendering the compounds represented by these formulas non-diffusible, and has a substituted or unsubstituted carbon number of 8 to 30. Alkyl group, acylamino group having 8 to 30 carbon atoms, acyl group having 8 to 30 carbon atoms, 8 carbon atoms
An acyloxy group having 30 to 30, an alkoxy group having 8 to 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, and an alkoxy group having 8 to 30 carbon atoms and an alkoxycarbonyl group having 8 to 30 carbon atoms Represents a direct bond ballast group selected from the group, a carbamoyl group represented by the following formula (A) or a sulfamoyl group represented by the following formula (B). (In the above formula, Ball 'represents the direct bond ballast group, R ³ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group or an aryl group, and L represents a divalent alkylene group or phenylene group. Alternatively, it represents a divalent arylthio group, and m represents 0 or 1. However, when R ¹ is a non-diffusible group, Ball may not be present. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. R ² is a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group. Represents a group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group or an arylthio group. n represents an integer of 0 to 5, and when n is 2 to 5, R ^{2 s} may be the same or different, and may combine with each other to form a ring. It should be noted that when Y represents the atomic group necessary to complete the naphthalene nucleus, Ball and R ² can be attached to any of the ring systems so formed. ｝