JPS62150240A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat-developable photosensitive material small in heat fog and high in sensitivity by using photosensitive silver halide core/shell type grains having a silver iodide content of 4-40mol%, and a photosensitive material containing a specified N-containing heterocyclic compound. CONSTITUTION:The silver halide photosensitive layer contains photosensitive silver halide core/shell type grains having a silver iodide content of 4-40mol%, and the photosensitive material contains one of N-containing heterocyclic compounds represented by formulae I and II in which X<1> is -O-, -S-, -Se-, or =N-; Z is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; each of L<1> and L<2> is a divalent group; and X<2> is C or N for forming an unsaturated ring. Said compound may be added to any of the constituent layers of the heat-developable photosensitive material or any plural ones of them, and, preferably, to the photosensitive layer containing photosensitive silver halide, and a proper amount of it to be added is generally 10<-7>-10<-1>mol per mol of silver halide.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a heat-developable photosensitive material, and more particularly to a heat-developable photosensitive material with improved fog during heat development (thermal fog).

[Conventional technology]

A method in which the development step for obtaining a color image is performed by dry heat treatment has many advantages over the conventional wet method in terms of processing time, cost, and concerns about pollution. Regarding heat-developable photosensitive materials in which the above-mentioned development process can be carried out by dry heat treatment, for example, Japanese Patent Publication No. 43-4921 and No. 43
There is a description in Publication No. 4924, which discloses a black and white type photothermographic material comprising an organic silver salt, silver halide and a reducing agent. Attempts have also been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, JP-A-5
No. 7-179840, No. 57-186744, No. 57
-No. 198458, No. 57-207250, No. 58-
No. 40551, No. 58-58543, No. 58-792
No. 47, and Japanese Patent Application No. 57-122596 and No. 57-13.
No. 2884, No. 57-179236, No. 57-229
No. 671, No. 57-229674, No. 57-2296
No. 75, No. 58-33363, No. 58-33364, No. 58-34083, JP-A-58-116537, No. 58-123533, No. 58-149046,
There is also No. 58-14947. The basic composition of a color type heat-developable photosensitive material for obtaining this color image consists of a photosensitive element and an image receiving element, and the photosensitive element basically consists of a photosensitive silver halide, an organic silver salt, a reducing agent, a dye donor, and It consists of a binder. In addition,
In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense. In the former black-and-white type, optical information is given to the photosensitive silver halide by image exposure, and during thermal development, the exposed photosensitive silver halide and the reducing agent in the photosensitive layer are present in the vicinity. The contact action of the silver halide causes an oxidation-reduction reaction to produce silver, and the exposed areas of the photosensitive layer turn black to form a silver image. In the color type, optical information is given to the photosensitive silver halide by image exposure, and during thermal development, the optical information is transferred between the organic silver salt and the photosensitive silver halide under the action of a reducing agent. Dissolution physical development was performed and worked,
Alternatively, the dye that forms the image is released or formed by the reaction of the reducing agent that has not acted with the dye-providing substance. The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image. In recent years, as an exposure means for heat-developable color photosensitive materials,
Light sources with low exposure illuminance such as LEDs, CRTs, FOTs, and semiconductor lasers are being tried. On the other hand, it is necessary to shorten the time required to obtain an image, and particularly in photosensitive materials that are rapidly processed such as heat-developable photosensitive materials, it is further desired to shorten the exposure time. Therefore, it is desired to increase the sensitivity of heat-developable color photosensitive materials. As a technique for increasing sensitivity, it is possible to increase sensitivity by increasing the critical content in silver halide, but it has become clear that increasing the critical content increases thermal fog. Ta. To address this problem, many thermal fog inhibitors have been proposed to reduce thermal fog. For example, U.S. Pat.
9.903 mercury compound, West German patent fjS2.402
．． N-halogen compound of No. 161, No. 2,500,5
peroxide of No. 08, sulfur compound of U.S. Pat. No. 2,617.907, palladium compound of U.S. Pat. No. 4,102.312, sulfine N1w of Japanese Patent Publication No. 53-28417.
1. Research Disclosure+-No. 169077
, flucaptotriazole disclosed in U.S. Patent No. 169079, and 1.2.4-triazole disclosed in U.S. Pat. However, these thermal anti-capri agents are extremely harmful to the human body, and their anti-capri effects are small against silver halide grains with a high silver iodide content, so no effective anti-capri agents have yet been found. .

[Purpose of the invention]

Therefore, an object of the present invention is to solve the above-mentioned drawbacks and to provide a heat-developable photosensitive material that has low thermal fog and high sensitivity.

[Structure of the invention]

The object of the present invention is to provide a heat-developable photosensitive material having at least a photosensitive silver halide, an organic silver salt, a reducing agent, and a noguing agent on a support, with a silver iodide content of 4 to 4 as the photosensitive silver halide. The photosensitive material has 40 mol% core/shell particles and has the following general formula (1) or (If).
This is achieved by a photothermographic material characterized by containing a nitrogen-containing heterocyclic compound represented by: General formula (T), Z represents a nonmetallic atomic group necessary to form a 5-shell or 6-shell heterocycle, 1 and L2 each represent a divalent group, and In and n are each 0 or 1. 11]2 and R4 may be the same or different and each represents a hydrogen atom, a halogen atom, a mercapto group, a hydroxyl group, a carboxylic acid group or its salt, a sulfonic acid group or its salt, or each substituted or unsubstituted represents an alkyl group or an aryl group, and at least one of n', n' and R4 is at least one selected from a hydroxyl group, a carboxylic acid group or a salt thereof, and a sulfonic acid group or a salt thereof. R3 represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group. The heterocycle represented by Z may have a fused unsaturated ring,
For example, benzoxazole ring, benzothiazole ring,
Examples include a pencyimiguzole ring, a benzoselenazole ring, a quinazoline ring, a thiazole ring, a triazole ring, a thiadiazole ring, and a tetrazole ring. Examples of divalent groups represented by L' and L2 include alkylene groups (e.g., methylene, ethylene, propylene, etc.)
, arylene group (eg lrρ-phenylene, +a −
Examples thereof include phenylene, o-phenylene l, imino group, carbonyl group, sulfonyl group, oxy group, and groups composed of these groups (for example, carbonyl group mi/, sulfonyl group mi7, arylene imif group, etc.). Examples of the alkyl group represented by R1,1(2 and R4 include methyl group, ethyl group, i-propyl group, trifyl group,
Examples of the aryl group include a phenyl group, a p-)'j group, and a naphthyl group. However, when L+ or L2 is an imino group, R1 and/or R2 connected to this imino group does not contain a hydrogen atom. Examples of the quaternary ammonium group represented by R3 include a trimethylammonium group, and examples of the quaternary phosphonium group include a triethylphosphonium group. Preferred examples of the compounds of the present invention represented by the general formula [■] are shown below, but the scope of the present invention is not limited thereby. The following margin is white [Example of compound] CL to □N 1-24 S. General formula (U) In the formula, 12 represents a carbon atom or a nitrogen ring atom forming an unsaturated ring, Z' represents a group of nonmetallic atoms necessary to form a 5-shell or 6-shell heterocycle, L3 and L4 each represents a divalent group, ■ and 11 represent 0 or 1, R5 and R6 may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a hydroxyalkyl group, a carboxylic acid group, or a salt thereof. , represents a sulfone ring group or a salt thereof, an ami7 group, or a substituted or unsubstituted alkyl group or aryl group, and at least one of R5 and R6 is a hydroxyalkyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof and at least one selected from ami7 groups. The heterocycle represented by 2' may have an unsaturated ring bonded to it, and examples thereof include a benzotriazole ring and a tetrazaindene ring. Examples of divalent groups represented by L3 and L4 include general formula [I]
Examples include the groups listed for Ll and L2. Examples of the alkyl group represented by R5 and R6 include a methyl group, ethyl group, propyl group, trifluoromethyl group, etc., and examples of the aryl group include a 7-enyl group, p-)
Examples include 'J' group and naphthyl group. However, when L2 or Ll is an oxy group, R5 and/or R@ linked to the oxy group do not contain a hydrogen atom. Preferred examples of the compounds of the present invention represented by the general formula (If) are shown below, but the scope of the present invention is not limited thereby. [Compound Example] II-6■-7 Nll. The compound represented by the general formula [1] or [■] of the present invention can be synthesized by a conventional method. For example, Chemisohe 8erichte 8
6゜pp, 314 (1953) and Canadian Journal of Chemistry"Canadian J
ournol of CI+eIIIistry″37
．． pp. 101 (1959), Chanal et al.
Of Chemical Society 4-”JOHBI of C
henical 5ociety″49tpp, 174
8 (1927), and JP-A Nos. 50-89034 and 53-28426. The compound represented by the general formula [I3 or [■] of the present invention may be added to any oval waste of the photothermographic material,
Although it can be added to one or more layers, it is preferably added to a photosensitive layer containing photosensitive silver halide. These compounds can be used alone or in combination of 2s or more, and the amount used is not limited depending on the M class of photosensitive silver halide and ammonium salt or the mixing ratio, but in general silver halide 1 A range of 10-7 to 10-1 mol per mole is appropriate, preferably 10-5 to 10-2 mol. The timing of addition of the compound represented by formula (1) or (II) of the present invention is from the start of precipitation of silver halide grains to the time when the emulsion containing the silver halide grains is coated. It can be any time of the year. Further, any method known in the US can be used for the addition, but it is particularly preferable to add the compound in the form of an acid or salt dissolved in water, an organic solvent such as methanol, or a mixed solvent thereof. A core with a silver iodide content of 4 to 40 mol% in the present invention/
Shell-type silver halide grains are grains having a surface layer, or shell, which is different in silver halide composition from the interior, and the interior, or core, of such shell is a multilayer MMIt structure consisting of layers that are different in silver halide composition, etc. It may have. A preferred embodiment of the present invention is that the thickness of the shell covering the core in core/shell type silver halide grains is 0.05 to 90%, particularly 1 to 80%, of the finished silver halide grain size. Also, the silver iodide content of the core is 4 to 20 mol%, and the silver iodide content of the shell is 0 to 6 mol%, and in particular, the silver iodide content of the core is 4 to 20 mol%. The silver iodide content is 2 mol% or more higher than the silver iodide content. A core with a silver iodide content of 4 to 40 mol% in the present invention/
A particularly preferred silver iodide content of the shell-type silver halide grains is 4 to 20 mol%. Furthermore, the grains are surface latent image type silver halide grains, and the grain size is preferably 0.0.
1 to 0.4 μm, more preferably 0.05 to 0.4 μm
It is 1m. There are no particular restrictions on the silver halide composition of the grains other than the silver iodide content mentioned above, but a preferred silver halide composition is silver iodobromide and silver chloroiodobromide. The crystal shape of the photosensitive silver halide grains of the present invention may be a regular crystal shape such as a cube, an octahedron, or a tetradecahedron, or an irregular crystal shape such as a spherical shape or a plate shape. It can also be something that has a shape. In these particles, any ratio of 1loo1 side to 1llll1 side can be used. Moreover, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed. Even when the core/shell type silver halide grains of the present invention are used as is, they also have different average grain sizes of 2! ! One or more of these may be blended at any time after grain formation to obtain a predetermined gradation level, and may also be used in combination with silver halide grains other than those of the present invention. It is preferable that the proportion of the core/shell grains of the present invention in the photosensitive silver halide is large, and it is most preferable that substantially the entire amount is the core/shell grains of the present invention. The silver halide emulsion having silver halide grains having a shell according to the present invention can be produced by covering a shell with a /10 dended grain contained in a monodisperse emulsion as a core.
JI construction is preferred. The dispersion emulsion used herein means that the photosensitive silver halide grains contained in the emulsion have a uniform grain morphology, and the standard deviation of the grain size distribution of the grain group is divided by the average grain size (i.e., Variation coefficient of diameter distribution a) Power bow 5% or less (preferably 13% or less)
emulsion. Here, the particle size is the diameter when the particle is spherical, and when the particle is other than spherical, the diameter when its projected image is converted into a circular image with the same area. In order to make the core a monodisperse silver halide grain, 11A[
Particles of a desired size can be obtained by the double jet method while keeping l constant. Further, for highly monodisperse silver halide emulsions, the method described in JP-A-54-48521 can be applied. Among these methods, a preferred method is to add a potassium iodobromide-gelatin aqueous solution and an ammoniacal nitrate aqueous solution to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. do. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pl+, 1]8 g, temperature, etc. By sequentially growing shells using the above-mentioned core grains with good monodispersity according to a known manufacturing method for monodisperse emulsions, monodisperse silver halide grains that can fully obtain the effects of the present invention can be obtained. A silver halide emulsion can be obtained. The light-sensitive silver halide emulsion used as the light-sensitive silver halide in the present invention may be chemically sensitized by any method in the field of photography. Such sensitization methods include gold sensitization, gold sensitization,
Various methods include sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The photosensitive silver halide emulsion prepared as described above is most preferably applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another photosensitive silver halide, a photosensitive silver salt-forming component is allowed to coexist with an organic silver salt described below, and a photosensitive silver halide is formed in a part of the organic silver salt. /shell-type silver halide grains.As the photosensitive silver salt forming component used in this preparation method, inorganic) 10 denides, for example, halides represented by M represents an H atom, NH, group, or metal atom, X represents C111%Br or I, n represents 1 when M is an H atom, NH, or group, and represents the valence when M is a metal atom. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, lithium, strontium, barium, zinc, cadmium, mercury, aluminum, insium, lanthanum, ruthenium, thallium, germanium, tin, lead, 7-inch, bismuth,
Examples include chromium, molybdenum, tungsten, manganese, rhenium, iron, fuvardite, nickel, lonotum, paranoum, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g., K, PtCf
1i+ to 2PtBra+II^u CQ,, (NH-
)2 TrCQs, (8114)z rr CQ
g. (NH4)2 RLI CQg, (NH4)Ju C(
Is, (NH-)-R1+ C(la-(Nt14)s
RhBr5, etc.), onium halides, quaternary ammonium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide), tetraethyl 7-year-olds Quaternary 7 male 7 onium halides such as 7 onium bromide, pennoethylmethylsulfonium bromide, 1-
3f & sulfonium halides such as ethylthi7zolium bromide), halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-
2-Methylpropane l, N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromo heptatalymide, N-bromoacetamide, N-iodosuccinimide, N-bromo heptalanonone, N- Chloro 7-tafcine/N, N-bromoacetanilide, N, N
-dibromobenzenesulfonami I', N-furomo N
-methylbenzenesulfonamide, 1.3-'/bromo-4,4-dimethylhyguntoin, etc.), other halogen-containing compounds (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2- Examples include bromoethanol (¥?). These photosensitive silver salt-forming components and photosensitive silver halides can be used in combination in various methods, and the amount used is preferably o, oot, ~50 g per 1+' per layer, and more preferably Preferably 0.1f1 to 10g
It is. The heat-developable color photosensitive material of the present invention only needs to have at least one layer containing the above-mentioned core/shell particles and the compound represented by the above-mentioned general formula [1) or (II). , green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In the above case, the blue-sensitive silver halide, green-sensitive silver halide, and red-sensitive silver halide used, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex, (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, birinone, oxazole, thiazole, selenazole, and imidazole are more preferable.Such nuclei include a furkyl group, an alkylene group,
It may have hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl or enamine groups capable of forming fused carbocyclic or heterocyclic rings, and may be symmetrical or asymmetrical. , the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, the merocyanine dye may have an acidic nucleus such as a thiohyguntoin nucleus, a logenine nucleus, an oxazolidine nucleus, a barbylic acid nucleus, a thiazolinthione nucleus, a malononitrile nucleus, or a pyrazolone nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfofurkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, 7 scorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2.933,
A supersensitizing additive that does not absorb visible light, such as those described in the specifications of No. 390 and No. 2,937,089, can be used in combination. The amount of these sensitizing dyes added is 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide. More preferably l
Xl0-'mol-lXl0-'Dye-donating substances that can be used in the present invention are those that participate in the reduction reaction of silver halides and/or organic silver salts and form diffusible dyes as a function of the reaction. That's fine. Depending on their reaction mode, the dye-donor can be a negative-type dye-donor (i.e., which forms a negative dye image when negative-working silver halide is used) or a negative-type dye-donor (i.e., forms a negative dye image when negative-working silver halide is used). It can be classified as a Bot-type dye-donor that acts on a function (i.e., it forms a Bot-type dye image when a Negative-type silver halide is used). Negative dye-providing substances are further classified as follows, and any of these can be used in the present invention. Each dye-providing substance will be further explained. As the reducing dye releasing compound, for example, the following general formula (1
) are listed. General formula (1) %Formula% (1) In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of silver halide and/or organic silver salt, and Dye is a diffusion It is a pigment residue. Specific examples of the above-mentioned reducible dye-releasing compounds include JP-A No. 5
No. 7-179840, No. 58-116537, No. 59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
No. 59-123837, No. 59-185054, No. 59-15959, etc., and examples thereof include the following compounds. Exemplary dye-providing substances Examples of other reduced dye-releasing compounds include compounds represented by the following general formula (2) below. General formula (2) % formula % represents a loxyl group or an amine 7 group, Dye is general formula (1)
It is synonymous with Dye in . Specific examples of the compound represented by the general formula (2) are shown in JP-A-59-124329. As a coupled dye-releasing compound, the following general formula (
Examples include compounds shown in 3). General formula (3) %Formula% (3) In the formula, C13 is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a divalent The bond between C1)1 and J is cleaved by rli upon reaction with the oxidized form of the reducing agent. n represents 0 or 1, and Dye has the same meaning as defined in general formula (1). Further, C1l+ is preferably substituted with various pallast groups in order to make the coupled dye-releasing compound non-diffusible, and the pallast group has 8 or more carbon atoms ( more preferably 12 or more organic groups, or aqueous groups such as sulfo groups and carboxyl groups, or 8 or more (more preferably
More preferably, it is a group having both carbon atoms (12 or more) and a hydrophilic group such as a sulfo group or a carboxy group. Another highly preferred pallast group is a polymer chain. Specific examples of the compound represented by the above general formula (3) include JP-A-57-186744 and JP-A-57-122596.
For example, the following compounds may be mentioned. Can be mentioned. Exemplary dye-providing substance coupling dye-forming compounds include the following general formula (4
) are listed. General formula (4) % formula %) (4) In the formula, Cp2 is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusive dye. , X represents a divalent bonding group, and Q represents a ballast group. The molecular weight of the coupler residue represented by C112 is preferably 700 or less, more preferably 500 or less, for the diffusivity of the formed dye. It is. Further, the ballast group is preferably the same as the ballast group defined in general formula (3), and particularly has 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Groups having both are preferred, and polymer chains are more preferred. As the coupling dye-forming compound having this polymer frequency, a polymer having a repeating unit derived from a monomer represented by the following general formula (5) is preferable. General formula (5) % formula %) (5) In the formula, Cl1z and X have the same meanings as defined in general formula (4), Y represents an alkylene group, arylene group, or aralkylene group, and Z L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group; Ω represents O or 1; Specific examples of coupling dye-forming compounds represented by general formulas (4) and (5) include JP-A-59-1.2433
No. 9, No. 59-181345,! H 58-109
No. 293, No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
Examples include those described in No. 7, etc., and include, for example, the following compounds. Exemplary dye-providing substance 00H Polymer [phase] υ ■ ■ CHz In the above general formulas (3), (4) and (5), C
To explain the coupler group defined by pI or C112 in more detail, groups represented by the following general formulas (6) to (15) are preferable. General formula (6) General formula (7) General formula (8) General formula (9) General formula (14
) General formula (15) (6) to (15)
In the formula, R', R2, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkylokynecarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group. group, carbamoyl group, sulfamoyl group, acyloxy group, amine 7 group, alkoxy group, aryloxy group, cyano group, ureido group, furkylthio group, 7
It represents a 1J-ruthio group, a carboxyl group, a sulfo group, or an i-aryl group, which further includes a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, a 7-aryloxy group, It may be substituted with an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like. These substituents are selected depending on the purpose of Cp+ and C10, and as mentioned above, in Cpl, one of the substituents is preferably a ballast group, and in CI)2, it is preferable to increase the diffusivity of the dye formed. The substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less. As a Bott type dye-donor substance, for example, the following general formula (1
There are oxidizable dye-releasing compounds represented by 6). General formula (16) In formula (16), W' represents an atomic group necessary to form a quinone ring (which may have a substituent on this ring), and R' is an alkyl group or hydrogen atom, C is ■ -N -C(I'! '← (wherein, R6 represents a furkyl group or a hydrogen atom, and R7
represents an oxygen atom or -N-. ) or -802-, r represents O or 1, and Dye has the same meaning as defined in general formula (1). Examples of this compound are described in JP-A-59-166954 and JP-A-59-154445, and include the following compounds. As for the exemplified dye-donating substances, the following general formula (17)
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by: General formula (17) In formula (17), l112 represents a collection of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R5, B, r and Dye are General formula (16)
It has the same meaning as defined in . Specific examples of this compound are described in the specifications of JP-A-59-124329 and JP-A-59-154445, and include the following compounds. Exemplary dye-donor substance CHff Still another positive dye-donor substance is represented by the following general formula (
Examples include compounds represented by 18). General formula (18) (18) In the above formula, l112, R5 and Dye have the same meanings as defined in general formula (17). Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds. General formulas (1), (2), (3), (16), (1
The residue of the diffusible dye represented by Dye in 7) and (18) will be explained in further detail. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less for the sake of dye diffusivity, and includes azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, Examples include residues such as quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dye residues may be in a temporary short-wavelength form that can be colored during thermal development or photographing. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in
Chelatable dye residues described in No. 9-48765 and No. 50-124337 are also preferred. These dye-donating substances may be used alone, or 2F1
One or more may be used in combination. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers. For example, the amount used is 0.005 g to 50 g per 1 I62, preferably 0.1 g to 10 g. Can be used. 0.005g to 10g, preferably 0.1g to 5.0g for 1+a2
Can be used. The dye-providing compound can be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material by any method. For example, a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high boiling point solvent T 7 tallate, tricrenenorphosphate, etc.) and then subjected to ultrasonic dispersion, or an alkaline aqueous solution w1. (for example, a 10% aqueous solution of sodium hydroxide, etc.) and then neutralized with a mineral acid (for example, hydrochloric acid or nitric acid, etc.), or use an aqueous solution of an appropriate polymer (for example, gelatin, polyvinyl butyralide, etc.). , polyvinylpyrrolidone, etc.) using a ball mill before use. As the reducing agent used in the heat-developable photosensitive material of the present invention, those commonly used in the field of heat-developable color photosensitive materials can be used, such as those described in U.S. Pat. , same No. 3.784,328
The specifications of each issue, as well as R D No. 12146 and R D No.
o, 15108, same No. 15127 and JP-A-56-27132, p-phenylenediamine type and p-ami/phenol type developing agents, 7 male 7 oleamide 7 ethyl type and sulfonamide 7 ethyl type developing agents , and hydrazone color developing agents. Also, U.S. Patent No. 3,
342,599, 3,719.492, JP-A-53-135628, JP-A-54-79035, etc., color developing agent precursors and the like can also be advantageously used. As a long-awaited preferable reducing agent, JP-A-56-146133
Examples include reducing agents listed in No. Other reducing agents as described below can also be used. For example, 72/-l M (e.g. +1-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-p-7minol, etc.), sulfonamide 7er/-ols [e.g. 4-
Benzenesulfonamide 7 ether, 2benzenesulfonamide 7 ether, 2゜6-fuchloro-4-benzenesulfonamidophenol, 2.6-nopromo 4-(
p-) luenesulfonamide) 7 ether, etc. or polyhydroxybenzenes (e.g. hydroquinone, t
ert-butylhydroquinone, 2,6-methylhydroquinone, arohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatefur, etc.)
, naphthols (e.g. α-su7tol, β-su7tol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylenebisnaphthols [e.g. 1,1'-dihydroxy-2,2' -binaphthyl, 6,6'-dibromo-2,2'-nohydroxyi,i'-binaphthyl, 6,6-sinitro2.2
'-Nohydroxy-1,1'-binaphthyl, 4,4'-
Dimethoxy-1,1'-nohydroxy-2,2'-binaphthyl, bis(2-hydroxy-1-7thyl)methane, etc. 1, methylenebisphenols [e.g. 1,1-bis(2-hydroxy-3,5- trimethyl 7enyl)-3,
5,5-)trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)
Methane, 1,1-bis(2-human axy-3,5-no-Lert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-5-methylphenyl)-4-methyl 7er7-el, α-phenyl-α, α-bis(2-human mixi 3,5-noter
t-butylphenyl)methane, α-phenyl-αta-
Bis(2-hydroquine-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-tmethyl7enyl)-2-methylpropane,
1.1.5.5-tetrakis(2-hydroxy-3,5
-trimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)furopane, 2,2-bis(4-hydroxy-3-methyl-5-jert-butylphenyl)propane, 2,2
-bis(4-hydroxy-3,5-di-Lert-butylphenyl)propane, etc. 1, ascorbic acids, 3-pyrazolidones, ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and para-7-functional nyrefdiamines. It will be done. These reducing agents can be used alone or in combination of two or more. The amount of ``a'' to be used depends on the S type of the photosensitive silver halide used, the type of organic acid silver salt, and the type of other additives, but it is usually 0.5% per mole of the dye-providing substance. The amount ranges from 0.05 to 10 mol, preferably from 0.1 to 5 mol. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural binders such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, and heptadated gelatin. One or more of these polymeric substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a water-based polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in Japanese Patent Application No. 104249/1982. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer of vinylpyrrolidone with one or more other monomers that can be copolymerized (including kraft copolymers). ), these polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight of 1,000 to
400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl alcohols, (meth)acrylamides, vinyl pyrrolidone, Examples include vinyl monomers such as polyols and vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (wt%, same hereinafter) of the composition ratio. A preferred example of a dark copolymer has a molecular weight of 5,000
It is a dispute between 0 and 400.000. The gelatin may be obtained by lime treatment or acid treatment (eg, ossein gelatin, pickskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins). It is preferably 10 to 90%, more preferably 20 to 60%, and the polymer of the present invention preferably accounts for 5 to 90%, more preferably 10 to 80%. may contain a polymeric substance of
Gelatin and a mixture of polyvinylpyrrolidone with a molecular mi, ooo~400.000 and one or more other polymeric substances, gelatin and a molecular weight of 5,000~400°00
A mixture of 0 vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral,
Examples include polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and natural substances such as polysaccharides such as starch and gum arabic. These are 0-85%, preferably 0-70%
May be included. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand). The amount of binder used is usually 0.0 per m' of support.
05. ~100g, preferably 0. O1g~40
．． The binder is preferably used in an amount of 0.1 g to 10 g, more preferably 0.25 to 4 g, per 1 g of one unit of the dye-providing substance Moama. In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publications No. 43-4921, No. 44-26582, No. 45-18416, No. 45-12700, No. 45-
No. 22185, JP-A-49-52626, JP-A No. 52-3
No. 1728, No. 52-137321, No. 52-141
No. 222, No. 53-36224, No. 53-37610
No. 3,330,633, U.S. Patent No. 3,794
．． No. 496, No. 4.105, 451, No. 1J4.
No. 123,274, No. 4.168,980, etc. @
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behen[1, ff-<1-phenyltetrazolthio)acetate, etc. , silver aromatic carboxylates, such as silver benzoate, silver heptalate, etc.,
-26582, 45-12700, 45-18
No. 416, No. 45-22185, JP-A-52-317
No. 28, No. 52-137321, 911 No. 58-11
Silver salts of imino groups such as those described in No. 8638 and No. 58-118639, such as silver benzotriazole, silver 5-7cetamidobenzotriazole, silver 5-nitropenzotriazole, silver 5-chlorobenzotriazole, 5-/) silver quinbenzotriazole, silver 4-sulfobenzotriazole, silver 4-hydroxybenzosiliazole, silver 5-7mi/benzotriazole, silver 5-methylsulfobenzotriazole, silver 5-carboxybenzotriazole, silver imiguzole , berezimidazole silver,
6-2F lopenzimiguzol kite, pyrazole silver, urazole silver, 1.2.4-) lyazole silver, IH-tetrazole silver, 3-7mi/-5-bennorthio-1,2,4
- triazole silver, saccharin silver, 7 tarazine silver, 7
Silver talimide, etc. Silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptopenzimigzole, 3-flucapto-4-phenyl-1°2.4
-) Riazole silver, 4-hydroxy-6-/thiru 1.
3,3a,? -tetrazaindene silver and (15-/thi-7-hydroxy-1.2,3,4.6-bentazaindene silver).Among the above organic silver salts, imino group silver salts are preferred;
Particularly preferred are silver salts of benzotriazole derivatives, more preferably silver salts of sulfobenzotriazole derivatives. The organic silver salt may be used alone or in combination of two or more, isolated and used by dispersing it in a binder by an appropriate means, or the silver salt may be prepared in a suitable binder. However, it may be used as is without isolation. The amount of the organic silver salt used is preferably 0.1 to 5 mol, more preferably 0.3 to 3 mol, per 1 mol of the dye-donating substance unit. It is preferable that various heat solvents are added to the heat-developable photosensitive material of the present invention. The thermal solvent may be any substance that promotes thermal development and/or thermal transfer, and is preferably a substance that is solid, semi-solid, or liquid at room temperature and dissolves or becomes a solvent in the paint by heating. are urea derivatives (e.g., trimethylurea, trimethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide'''IP), polyhydric alcohols (e.g., 1,5-bentanediol, 1,6-bentanediol, 1,2-cyclohexaneol, pentaerythritol, trimethylrolethane, etc.), or polyethylene glycols.Detailed specific examples include the compounds described in W Application No. 104249/1983.These thermal solvents may be used alone or in combination of two or more. In addition to the above-mentioned components, various additives may be added to the photothermographic material of the present invention as necessary. For example, as a development accelerator, , U.S. Patent No. 3,220°8
40, same tJS No. 3,531,285, same tJS No. 4,01
No. 2,260, No. 4,060,420, No. 4.0
No. 88,496, No. 4.207,392, each specification a,
RD No. 15733, RD No. 15734, RD No. 15776, JP-A-56-130745
Alkali releasing agents such as urea and guaninium trichloroacetate described in Japanese Patent Publication No. 1970-12700, U.S. Pat.
-co-, -so□-, -5O described in No. 667.959
Non-aqueous polar solvent compound having - group, US Pat. No. 3,4
No. 38,776, Melt 7 Ohmer, U.S. Pat.
, No. 666.477, and polyalkylene glycols described in JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5
No. 020, No. 49-91215, No. 49-10772
No. 7, No. 50-2524, No. 50-67132, No. 50-67641, No. 50-114217, No. 52
-33722, 52-99813, 53-10
No. 20, No. 53-55115, No. 53-76020, No. 53-125014, No. 54-156523,
No. 54-156524, No. 54-156525, No. 54-156526, No. 55-4060, No. 55-
No. 4061, No. 55-32015, West German Patent No. 2,1
No. 40,406, fp12,147,063, Z
. No. 220.618, U.S. Patent No. 3.080,254;
Same No. 3,847゜612, Same No. 3,782.941, Same No. 3,994,732, Same No. 4,123,282
No. 4,201,582, which are compounds 7-taladinone, 7-talimide, pyrazolone, quinazolinone, N-hydroquinaphthalimide, benzoxazine, 7-toxazinone, 2,3-dihydro -7 thalanone, 2,3-dihydro-1,3-oxazine-2,4-dione, oxyvirinone, aminopyridine, hydroxyquine/phosphorus, ami/quinoline, incarbostyryl, sulfonamide, 2H-1,3- benzothiazine-2,4-(3H)dione, benzotriazine,
Examples include mercaptotriazole, nomercabutotetrazabentalene, heptacuric acid, na7talic acid, heptalaminic acid, etc.; mixtures of one or more of these with imiguzol compounds; A mixture of at least one acid or acid anhydride such as an acid and a 7-talanone compound, further, a mixture of 7-talanone and maleic acid, itaconic acid,
Examples include combinations of quinolinic acid, dentisic acid, and the like. Mata, * [[No. 58-189828
3-7 minnow-5-furcapto-1°2.4-) lyazoles and 3-7 cylamino-5-mercapto-1,2,4-) lyazoles described in No. 93460 are also effective. In addition, as anti-capri agents, hydroquinone derivatives (e.g., di-1-octylhydroquinone, dodecanylhydroquinone, etc.) described in Japanese Patent Application No. 59-56506, /% hydroquinone derivatives described in Japanese Patent Application No. 59-66380, and benzene ) It can also be preferably used in combination with IJ azole derivatives (eg, 4-sulfobenzotriazole, 5-1-lupoxybenzotriazole, etc.). In addition, as a stabilizer, a print-at preventive agent may be used at the same time, especially after the treatment.
Halogenated hydrocarbons described in No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromomethyl Examples include sulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyltriazine. Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
A post-treatment may be carried out using a sulfur-containing compound as described in No. 1 and No. 50-77034. Furthermore, U.S. Pat. No. 13,301.678, U.S. Pat.
506,444, 3.824.103 and 3,844,788, and U.S. Pat. No. 3.669.
, No. 870, No. 4,012,260, Pt54,
It may contain the actyl beta stabilizer precursor described in No. 060,420 and the like. In addition, sucrose, former 14Fe(So<)t” 12H2
The water release agent of No. 01 may be used, and furthermore, water may be supplied and heat development may be carried out as in VF Patent Publication No. 56-132332. In addition to the above-mentioned components, the light-sensitive material of the present invention may further contain various additives such as a spectral sensitizing dye, an antihalation dye, a fluorescent whitening agent, a hardening agent, an antistatic agent, a plasticizer, and a spreading agent. , coating aids, etc. can be added. Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
Post-treatment may be carried out using a sulfur-containing compound as described in No. 50-77034. Furthermore, U.S. Patent No. 3,301,678, fpJ
No. 3,506,444, No. 3,824,103, and No. 3,844,788;
, 669,670, 4.012.260, 4,060,420, and the like. The support used in the heat-developable photosensitive material of the present invention includes:
Examples include polyethylene film, cellulose acetate film, polyethylene tere-7-thalerate film, synthetic plastic films such as polyvinyl chloride, and paper supports such as photographic base paper, printing paper, baryta paper, and Lennon coated paper. When the heat-developable photosensitive material of the present invention is a color type, basically (1) photosensitive silver helodenide, (2)
It is preferable to contain a dye-providing substance, (Ni elemental compound) and (4) a binder, and further contain (5) an organic silver salt if necessary. However, these are not necessarily contained in a single photographic constituent layer. It is not necessary, for example, the photosensitive layer is divided into two layers, the components (1), (3), (4), and (5) are contained in one photosensitive layer, and the components adjacent to this photosensitive layer are The dye-providing substance (2) may be contained separately in two or more photographic constituent layers as long as they can react with each other, such as by containing the dye-providing substance (2) in the layer on the other side. It may be divided into two or more layers such as a layer and a low-sensitivity WI layer, and may further have one or more photosensitive layers with different color sensitivities, or an overcoat layer and an undercoat layer. , a backing layer, an intermediate layer, or various photographic constituent layers such as filter waste.The heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer and other photographic constituent layers of the present invention A photosensitive material can be prepared by preparing each coating solution and using various coating methods such as a dipping method, an air knife method, a curtain coating method, or a hopper coating method described in US Pat. No. 3,681,294. Furthermore, if desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761.791 and British Patent No. 837,095. The above-mentioned components used in the constituent layers are coated on a support, and the thickness of the coating after drying is preferably 1 to 1,000 μm, more preferably 3 to 1,000 μm.
It is 20 μ-. The heat-developable photosensitive materials of the present invention include color photosensitive materials and monochrome photosensitive materials. An example of the latter is a black photosensitive material that uses a dye-donating substance in which the diffusible dye produced as a result of thermal development is a black dye. After the heat-developable photosensitive material of the present invention is imagewise exposed as it is,
Usually 80°C to 200°C, preferably 102°C to 170°C
at a temperature range of 1 second to 180 seconds, preferably 1.5
Color development can be achieved by simply heating for 120 seconds. Further, if necessary, the film may be developed with a water-impermeable material in close contact with the film, or it may be preheated at a temperature in the range of 70° C. to 180° C. before exposure. Various exposure means can be used for the photothermographic material according to the present invention. A latent image is an image of radiation including visible light! ! ! ! Obtained by exposure to light. Generally, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, it is also possible to provide a conductive layer in the photosensitive material of the present invention or in the image receiving layer (element) for thermal imaging to utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including preheating and then reheating, heating at a high temperature for a short period of time, or at a low temperature for a long period of time, continuously increasing, decreasing, or repeating, and even heating without heating. Although continuous heating is possible, a simple pattern is preferable, and a method in which exposure and heating proceed simultaneously may also be used. In the present invention, as the image-receiving layer that receives the diffusible dye imagewise formed by imagewise exposure and heat development of the photothermographic material, those commonly used in this field can be used, such as paper. , cloth, plastic, etc. can be used, but preferably a support is used in which an image-receiving layer containing a mordant or a compound having dye-receiving ability is provided on the support. As a long-awaited preferred image-receiving layer, Japanese Patent Application No. 1986-
Layer made of polyvinyl chloride and v as described in No. 97907
Examples include a layer made of polycarbonate and plastic cutting described in Japanese Patent No. 128,600/1983. The image-receiving layer may be provided on the same support as the photographic constituent layer, in which case it may have a structure that can be peeled off from the photographic constituent layer after the dye has been transferred, or it may be provided on a separate support. There is no particular restriction on its formation, and any technique can be used.

【Example】

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these embodiments. Example 1 First, a comparative silver bromide emulsion (emulsion Δ) was prepared by the following method.
was prepared. JP-A-57-92523, JP-A No. 57-92
Using the mixer shown in No. 524, a Δ solution containing 20 g of ossein gelatin, 1000 z1 of distilled water, and ammonia dissolved therein, and 500 zt of an aqueous solution containing 1.1 mol of potassium bromide were prepared at 50°C. Solution B and solution C containing 1 mole of silver nitrate and ammonia were added at the same time while keeping pAg constant. B liquid and fJj! was adjusted by controlling the addition rate. The obtained silver halide grains were octahedral grains with an average grain size of 0.3 μ+B and a coefficient of variation of grain size distribution of 8%. This emulsion was washed with water and desalted. The yield of emulsion was 8001N. In addition, three types of emulsions B-D having different silver iodide contents were i9-d by the following method. At 50°C, JP-A-57-92523, JP-A-57-92523;
Using the mixing agitation shown in No. 92524, ossein gelatin 209, distilled water 1000 shoulders! And in the ^ solution in which ammonia was dissolved, pAg was simultaneously added to solution B of 500xl of an aqueous solution containing potassium iodide and potassium bromide, and solution C of 8500x1 of an aqueous solution containing 1 mole of nitrate radical and ammonia. It was added while keeping it constant. The shape and particle size of the emulsion grains to be prepared were adjusted by controlling the addition rates of po, pAg, and solution B and cB. In this way, emulsions having the same regular octahedral shape but different silver iodide contents were prepared. (The coefficient of variation of the particle size distribution of each emulsion was 9%.) Each of these emulsions was washed with water and desalted. The yield of each emulsion was 800xl. Table 1 shows the average grain size and silver iodide content of each emulsion thus prepared. 1-□≧” Also, at 50°C, JP-A No. 57-92523,
Using the mixer shown in No. 7-92524, 20 g of ossein gelatin, 1000 zN and V ammonia of distilled water were dissolved in Solution A, and 500 y1 of Bfi, an aqueous solution containing potassium iodide and potassium bromide, and silver nitrate were added. A core emulsion was prepared by simultaneously adding 500 e of an aqueous solution containing 1 mol of ammonia and Solution C while keeping the pH constant. The shape and size of the core emulsion particles to be prepared are as follows:
It was adjusted by controlling the pH, 1]Δg, and the addition rate of solutions B and C. In this way, core emulsions having the same regular octahedral shape, average grain size, and different silver iodide contents were prepared. (The coefficient of variation of the grain size distribution of each core emulsion was 8%.) The silver halide grains of these core emulsions were coated with a silver halide shell in the same manner as described above to obtain positive Core/shell type emulsions E-1 of the present invention having the same octahedral shape and average grain size but different silver iodide contents were prepared. Each of these emulsions was washed with water and desalted to make 800 zl. The following margins\, -0,- The silver halide emulsion prepared above was mixed with the following sensitizing dye and V.
A photosensitive silver halide dispersion having the following composition was subjected to sulfur sensitization treatment with sodium thiosulfate in the presence of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. Silver halide (in terms of silver) 381g Gelatin 85g/2820yf 28.8g of silver 5-methylbenzotriazole obtained by reacting sensitizing dye 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent. , poly(N-vinylpyrrolidone) io,o, 4-sulfobenzotriazole sodium salt 1.33. was dispersed in an alumina ball mill to give a pif of 5.5, and 200 zf of an organic silver salt dispersion was prepared. Polymer dye-donor substance 3s, sg and the following hydroquinone compound 5.00. was dissolved in 200 il of ethyl acetate, and 1 part of a 5% by weight aqueous solution of Alkanol XC (manufactured by DuPont) was added.
The mixture was mixed with 720 zl of an aqueous gelatin solution containing 2411 and 30.5 g of phenylcarbamoylated gelatin (Russlow, Type 17819 PC), dispersed with an ultrasonic homogenizer, evaporated ethyl acetate, adjusted to pH 5.5 to 79511, and dye-donating. A substance dispersion liquid (1) was prepared. 23.3 g of the following developer (1), 1.10 g of the following development accelerator
g, poly(N-vinylpyrrolidone) 14. f3g and 0.50g of the following fluorosurfactant were dissolved in water, and p
1+5.5 to 250 ml, and a developer was prepared. Developer (1) Surfactant NaO,5-CH-C00CI+2(
CF2CF2)IHC11z(:OOCII2(CF2
CF2) ntl (m, n=2 or 3) 6.0 ozl of the photosensitive silver halide dispersion, 12.5 x 1 organic silver salt dispersion, dye-providing substance dispersion (1) 39,
8iffi, development [12,5z1 and a 2X 10-'' molar aqueous solution of the general formula (l or (If) of the present invention shown in Table 3 or its comparative compound ((a) and (b) below) 0, 7 ml of the hardener solution (tetra(vinylsulfonylmethyl)methane and taurine were reacted in a ratio of 1.:1 (IIJ amount ratio), and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin to form tetra(vinylsulfonylmethyl)methane.
Contains 3% by weight of (vinylsulfonylmethyl)methane. ) at 2.50m/3.80m/polyethylene glycol 300 (Kanto Kagaku) as a hot solvent. After addition, the amount of silver was 1.76 g on a 180 μm thick photographic polyethylene terephthalate film that was subbed.
A heat-developable photosensitive element 1 was prepared by applying a protective layer /1N made of a mixture of the phenylcarbamoylated gelatin and poly(N-vinylpyrrolidone) thereon. Polyvinyl chloride (n=1,00
An image-receiving element was prepared by applying a tetrahydro 7 run solution (Wako Pure Chemical Industries, Ltd.) so that polyvinyl chloride was 12y/+n2. The heat-developable photosensitive element was exposed to 1,600C, M, S through a step wedge, and then put together with the image-receiving element in a heat developing machine (Developer Monocle 277.
After heat development at 150°C for 1 minute at 3M Company,
When the light-sensitive element and image-receiving element were quickly peeled off, a magenta step wedge negative image was obtained on the polyvinyl chloride surface of the image-receiving element. The green reflection density of the obtained negative image was measured using a densitometer (PD8-65).
, Konishiroku Photo Industry Co., Ltd.! The relative sensitivity and minimum density (fog) are summarized in Table 3. It should be noted that the relative sensitivity here is the reciprocal of the exposure amount that gives a density of Capri+0.3, and is expressed as a relative value with the value of photosensitive element sample (1) set as 100. , -1 or less margin,
) From Table 3, it can be seen that in comparative light-sensitive elements (1) to (4), the sensitivity increases when a silver halide emulsion with a high silver iodide content is used, but the minimum density (fog) increases due to heat development. In addition, in photosensitive elements (5) and (6) using comparative compounds (a) and (b), the minimum density (capri) is high and also causes desensitization, whereas this photosensitive element It was proved that the photosensitive elements (8) to (16) using the emulsions and compounds of the invention not only have high sensitivity but also low minimum density, and have excellent characteristics. Light-sensitive elements using comparative emulsions (
7) has low sensitivity. Example 2 The silver halide emulsion prepared in Example 1 was mixed with the following sensitizing dye and 4-hydroxy-6-methyl-1,3,3a,7-
A photosensitive silver halide dispersion having the following composition was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of tetrazaindene. Sensitizing dye (2) Silver halide (sandwiched between silver) 381° Gelatin 85g 72820x1 Dye-providing substance ■30. Og was dissolved in tricresyl phosphate 30, Of and ethyl acetate 90.0 z (l), mixed with 460 ml of gelatin aqueous solution containing a surfactant as in Example 1, dispersed with a sonic homogenizer, and then ethyl acetate was distilled off. A dye-providing substance dispersion (2) was prepared by adding diluted water to 50011. The same photosensitive silver halide dispersion as used in Example 1 40.Ozl and organic silver salt dispersion 25.Ow, respectively.
e and dye-providing substance dispersion (2) 50. Mix Ozl and add polyethylene glycol 300 as a heat solvent.
(1511 Bundle Chemical) 4.20g, same hardener 3.0011e as in Example-1 and 1 of g7ninone trichloroacetic acid
A 0% water-alcohol solution 120.0x1 was added to give a silver content of 2.501 F/u onto a 180 μm thick undercoated polyethylene terephthalate film for copying JE.
The photothermographic element-2 was prepared by coating the photothermographic element 12 to obtain a photothermographic element-2. The following layers were sequentially coated on a transparent polyethylene terephthalate film having a thickness of 100 μm to prepare image receiving element-2. (1) A layer made of polyacrylic acid. (7,002/
+o”) (2) Layer consisting of cellulose acetate. (4,OO
g/1002) (3) Styrene and N-Pencil-N,N
A layer consisting of a 1:1 copolymer of -tumethyl-N-(3-maleimidopropyl)ammonium chloride and gelatin. (Copolymer 3.00g/v12, gelatin 3.00g/v12.
00g7m2) The heat-developable photosensitive element-2 was exposed to 1600e0M, S through a stepper, heated for 1 minute on a heat processor at 150°C, and then laminated with the image-receiving element-2 immersed in water; 50°C,
500-800g7cm2 was crimped for 30 seconds and quickly peeled off. The transmission density of the yellow transparent image obtained on the surface of the image receiving element was measured with a densitometer (PD8-65, Konishiroku Photo Industry Co., Ltd.), and the maximum density and minimum density (fog) are shown in Table 4. Note that the relative sensitivity here is the reciprocal of the exposure amount that gives a density of fog + 0.3, and is expressed as a relative value with the value of the photosensitive element (17) as 100. Similar to the results of Example 1, the photosensitive material of the present invention was similar to the comparative photosensitive material in a heat-developable color photosensitive material using a dye-donating substance that reacts with photosensitive silver halide to release a hydrophilic dye. It can be seen that the sensitivity and minimum concentration are superior.

【Effect of the invention】

According to the present invention, a type of silver halide containing a photosensitive silver halide, a major silver salt, a converter and a binder, which forms or releases a diffusible dye by heat development, and which transfers the dye to an image-receiving layer to obtain a dye image, is disclosed. The sensitivity-fog relationship of heat-developable photosensitive materials is improved. Applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment December 19, 1986

Claims (1)

[Scope of Claims] A heat-developable photosensitive material having at least a photosensitive silver halide, an organic silver salt, a reducing agent, and a binder on a support, wherein the photosensitive silver halide has a silver iodide content of 4 to 4.
1. A heat-developable photosensitive material having 40 mol% core/shell particles and containing a nitrogen-containing heterocyclic compound represented by the following general formula [I] or [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^1 is -O-, -S-, -Se-, >NR^
4 or =N-, Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and L^1 and L
^2 each represents a divalent group, m and n each represent 0 or 1
, R^1, R^2 and R^4 are each a hydrogen atom,
represents a halogen atom, a mercapto group, a hydroxyl group, a carboxylic acid group or its salt, a sulfonic acid group or its salt, or a substituted or unsubstituted alkyl group or aryl group, and at least R^1, R^2 and R^4 One is at least one selected from a hydroxyl group, a carboxylic acid group or a salt thereof, and a sulfonic acid group or a salt thereof. R^3 represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a quaternary phosphonium group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a group of nonmetallic atoms necessary to form, L^3 and L^4 each represent a divalent group, m and n represent 0 or 1, R
^5 and R^6 each represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group, or a substituted or unsubstituted alkyl group or aryl group, and R^
At least one of 5 and R^6 is at least one selected from a hydroxyl group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, and an amino group. ]