JPS63301034A - Thermodeveloping photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the sufficient optical density of the titled material by incorporating a specific cyclic compd. in at least one layer of photographic constituting layers. CONSTITUTION:In the titled material contg. a photosensitive silver halide, a reducing agent and a binder, the specified cyclic compd. is incorporated in at least one layer of the photographic constituting layers. Namely, said cyclic compd. is composed of the cyclic compd. which has at least one of the group selected from the groups comprising oxygen atom, -NR1- group (wherein R1 is hydrogen atom or alkyl group) and -NHCONH- group, etc., and contains at least two of sulfur atoms and a carbon chain as the essential component of a ring constituting component, and bonds said group and the sulfur atoms with the carbon chain, respectively. Thus, the image having the sufficient optical density is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-developable photosensitive material, that is, a photosensitive material from which an image is obtained by developing by heat treatment. In particular, it promotes development,
The present invention relates to a heat-developable photosensitive material that can obtain a sufficient maximum density.

[Background of the invention]

A photosensitive material (thermally developable photosensitive material) that can easily and quickly form an image by carrying out a dry process using heat in the development process is well known. No. 43-4924, [Fundamentals of Photographic Optics J (Published by Corona Publishing, 1879), 55]
Pages 3 to 555, and Research Disclosure Magazine June 1978 issue, pages 9 to 15 (RD-17029)
It is described in etc.

There are two types of heat-developable photosensitive materials: those that produce black-and-white images and those that produce color images. In recent years, in particular, attempts have been made to develop heat-developable color photosensitive materials that produce color images using various dye-providing substances.

In addition, there are various methods for heat-developable color photogenic materials, such as a method in which a color image is obtained by releasing or forming a diffusible dye through heat development and then transferring the dye (
Although this direction (hereinafter referred to as the transfer direction) requires an image receptor for transfer, it is superior in terms of image stability and clarity, and processing simplicity and speed. This transfer method heat-developable color photosensitive material and image forming method are known, for example, from Japanese Patent Application Laid-Open No.
No. 12431, No. 59-159159, No. 59-18
No. 1345, No. 59-229556, No. 60-295
No. 0, No. 61-52643, No. 61-61158,
No. 61-61157, No. 59-180550, No. 6
No. 1-132952, No. 61-132952, U.S. Pat. No. 4,595.652, U.S. Pat. No. 4,590.15
It is described in the specifications of No. 4 and No. 4,584.267.

However, in the heat-developable photosensitive materials that have been developed or proposed in the past, development is completed by the convenient means of heat treatment, and images with sufficient density may not always be obtained by this alone.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a heat-developable photosensitive material capable of obtaining images of sufficient density.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a heat-developable photosensitive agent containing a photosensitive silver halide, a reducing agent, and a binder, which is characterized in that a cyclic compound of the following types is contained in at least one of the photographic constituent layers. This is achieved using photosensitive materials.

Here, the above-mentioned cyclic compound refers to an oxygen atom, -NR, -(R
, is a hydrogen atom or an alkyl group) , -CONll-1
alkyl group) and -NHCONH-, and has at least two sulfur atoms and a carbon chain as essential ring constituent components; It is a cyclic compound connected by chains. Hereinafter, this cyclic thioether compound will be appropriately referred to as "the cyclic compound of the present invention".

A heat-developable photosensitive material is generally formed by coating at least one photographic constituent layer on a support.

In the heat-developable photosensitive material of the present invention, the photosensitive silver halide and the reducing agent do not necessarily need to be contained in the same layer. Furthermore, when the present invention is applied to color light-sensitive materials, some dye donors also serve as reducing agents, and it goes without saying that such dye donors can also be used as reducing agents in the present invention.

The heat-developable photosensitive material of the present invention can be embodied as a black-and-white photosensitive material, a monochromatic color photosensitive material, or a multicolor photosensitive material.

When producing a color photosensitive material, any dye donor can be used. Although it is preferred to use a diffusible dye donor,
It is not limited to that.

Further, it may be a transfer-type heat-developable photosensitive material, or it may be a non-transfer type photothermographic material. The transfer method is advantageous in terms of image quality. On the other hand, if the transfer method is not used, there is an advantage that an image receiving member is not required.

In the present invention, the cyclic compound of the present invention is contained in any layer of the photographic constituent layers.

The cyclic compound of the present invention will be explained in detail below.

As described above, the cyclic compound of the present invention has an oxygen atom, N
has at least one group selected from the group consisting of R+ (R+ is a hydrogen atom or an alkyl group), an alkyl group) and -NHCONH-, and has at least two sulfur atoms and a carbon chain as essential ring constituent components, and , is a cyclic compound in which the group and the sulfur atom are each bonded through the carbon chain.

In the above-mentioned cyclic compound, examples of the alkyl group represented by R, , R, include a methyl group and a propyl group.

Carbon chains that are ring constituents include methylene, ethylene,
Alkylene chains such as propylene and tetramethylene, 1,
2. Alkanetriyl chains such as 3-propanetriyl,
Alkadiene diylidene chains such as 1,3-butadiene diylidene, alkanediylidene chains such as butane diylidene, alkenylene chains such as 2-butenylene, cycloalkylene chains such as cyclohexylene and cyclopentylene, and arylene chains such as phenylene. Other examples include carbon chains in which two or more of the above-mentioned chains are bonded, such as alkylene arylene chains and alkylene cycloalkylene alkylene chains.

The cyclic compounds of the present invention include those having substituents such as halogen atoms (eg, fluorine and bromine) and hydroxyl groups.

Further, the cyclic compound of the present invention may be a monocyclic compound or a condensed polycyclic compound.

When a carbon chain bonds sulfur atoms, the number of carbon atoms in the chain portion of the carbon chain is preferably an even number (eg, ethylene, propylene, tetramethylene, 0-phenylene).

Further, the number of members of the cyclic compound of the present invention is preferably 12 or more members.

Exemplary compounds of the cyclic compound of the present invention are shown below.

1,,OVI 'VOOy'0
u The cyclic compound of the present invention is published in the Journal of Chemical Society Chemical Communication (J.
Chem, Soc, Chem, Commun,)
1970°1055, Angewante Hemi International Edition in English (
Angew.

Chem, Intern, Ed,) 13.14
9 (1974), Journal of Organic
Chemistry (J, Org.

Chem, ) 36.254 (1971), Chemical Review (CheIW, Rev,) '77, 5
13 (1977), British Patent No. 942°865, European Patent No. 216,973, and the like.

Examples of synthesis or synthesis schemes of exemplified compounds are shown below.

Exemplified Compound 5 Exemplified Compound 6 Exemplified Compound 10 Toluene-3,4-dithiol 48.8 g (0,3
13 moles).

A mixture of 20.7 g (0,313 mol) of 85% potassium hydroxide and 1-butanol with 50 axis β was heated to 116°C and heated to reflux while adding 22.5 g (0,313 mol) of bis(2-chloroethyl) ether. A solution of 157 mol) in 50 ml of l-butanol was added dropwise over 2 hours. The temperature of the mixture was lowered to 75°C, 20.7 g of 85% potassium hydroxide was added, and while heating and refluxing, bis(2-chloroethyl) was added.
22.5g of ether 50+nj! A 1-butanol solution was added dropwise over 1 hour. Refluxing was continued for an additional 4 hours. After acidifying with 3 ml of concentrated hydrochloric acid, 1-butanol was distilled off and water was added to keep the volume of the mixture constant.

The paste separated from the aqueous layer was mixed with chloroform 600+
Dissolve in s l 5% sodium hydroxide aqueous solution 400tm
Extracted with l. The chloroform solution was dried with calcium chloride and concentrated. Pasty residue 67.2 g to n-
It was extracted with hebutane and then with acetone. 4.2 g of white crystals of the target product were obtained from these extracts.

Exemplary Compound 11 The cyclic compound of the present invention is preferably used in silver halide photographic materials, but it can be added to non-photosensitive layers such as intermediate layers and protective layers in addition to the silver halide emulsion layer. Can be mentioned.

The amount to be added to the silver halide emulsion layer is as follows:
It is preferably 1.0X10-' to 0.2 mol, particularly preferably 1.0X10-' to 0.7 mol, per mol of S.

The addition time may be during the silver halide emulsion manufacturing process or before coating, but preferably during chemical ripening, at the beginning, at the end, and before coating.

When added to a non-photosensitive layer, lX per 100cd
10-' to 5 X 10-' mg is preferred.

The cyclic compound of the present invention may be used by adding one type of compound alone, or may use two or more types of compounds in combination. When two types of additives are used together, the total amount added is preferably within the above-mentioned range.

The heat-developable photosensitive material of the present invention can be embodied as a black-and-white photosensitive material or as a color photosensitive material. When producing a color photosensitive material, a dye-providing substance is used.

When the present invention is applied to a color photosensitive material, examples of the dye-providing substance include JP-A-62-44737 and JP-A-62-44737;
0-271117 and Japanese Patent Application No. 61-11563, such as the leuco dyes described in U.S. Pat. No. 475,441, or e.g. U.S. Pat. No. 4,235.957. Although an azo dye used in the heat-developable dye bleaching method described in et al. can be used as the dye-donating substance, it is more preferable to use a diffusible dye-donating substance that forms or releases a diffusible dye, and particularly It is preferable to use a compound that forms a diffusible dye through a coupling reaction.

Diffusible dye-providing substances that can be used in the present invention will be explained below. The diffusible dye-donor substance may be one that participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used if necessary, and can form or release a diffusible dye as a function of the reaction. well,
Depending on the reaction mode, negative-acting dye-donors that act on a positive function (i.e., those that form a negative dye image when using negative-working silver halide) and positive dye-donors that act on a negative function. dye-donors (that is, those that form a positive dye image when negative-working silver halide is used).

As a negative dye-donating substance, for example, U.S. Pat.
No. 63.079, No. 4,439.513, JP-A-59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
Examples include reducible dye-releasing compounds described in specifications such as No. 59-123837, No. 59-124329, No. 59-165054, and No. 59-164055.

Other negative dye-providing substances include, for example, U.S. Pat.
, No. 474.867, JP-A-59-12431, No. 5
No. 9-48765, No. 59-174834, No. 59-
No. 776642, No. 59-159159, No. 59-2
Examples include coupled dye-releasing compounds described in specifications such as No. 31540.

Yet another particularly preferred negative dye-donor substance is:
There is a Campling dye-forming compound represented by the following general formula (2).

General formula ■ Cp-←Jto→B) In the formula, Cp represents a functional group that can react with the oxidized form of a reducing agent (coupling reaction) to form a diffusive dye, and B represents a ballast group. represents. Here, the ballast group is a group that substantially prevents the dye-donating substance from diffusing during heat development processing, and includes groups (such as sulfo groups) that exhibit this effect depending on the nature of the molecule, and groups that exhibit this effect depending on the size of the molecule. Groups (such as groups with a large number of carbon atoms), etc. The coupler residue represented by Cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in order to improve the diffusibility of the dye formed.

The ballast group is preferably a group having 8 or more carbon atoms, more preferably 12 or more carbon atoms, or a sulfo group, a group containing both is even more preferable, and a group that is a polymer chain is even more preferable.

The coupled dye-forming compound having a group as a polymer chain is preferably one having a polymer chain having a repeating unit derived from a monomer represented by the general formula 〇 as the above-mentioned group.

In the remaining days, '.

:, ,+,l”:!, Knee contact type■ Cp→J←→YK→Z←→L) In the formula, cp and J have the same meaning as defined in the general formula ■, and Y is alkylene. β represents O or 1, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds represented by general formulas (1) and (2) include JP-A-59-124339 and JP-A-59-124339;
No. 9-181345, No. 60-2950, No. 61-5
No. 7943, No. 61-59336, U.S. Patent No. 4.6
No. 31,251, No. 4,650゜748, No. 4,65
No. 6,124, particularly U.S. Patent No. 4,656,124 and U.S. Patent No. 4,631.
．． Preferred are the polymeric dye-providing substances described in No. 251 and No. 4,650,748.

As a positive dye-donating substance, for example, JP-A-59-
Dye developer compounds described in publications such as No. 55430 and No. 59-165054, for example, JP-A-59-15444
Compounds that release diffusible dyes by intramolecular nucleophilic reactions described in publications such as No. 5 and No. 59-766954, cobalt complex compounds described in publications such as JP-A-59-116655, or, for example, JP-A-59-116655. No. 59-124327,
There are compounds that lose their dye-releasing ability when oxidized, as described in publications such as No. 59-152440.

In order to improve the diffusibility of the dye, the residue of the diffusible dye in the dye-providing substance used in the present invention preferably has a molecular weight of 800 or less, more preferably 600 or less; Examples include residues of dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like. These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in JP-A-59-48765 and JP-A-59-48765.
A preferred embodiment is a chelatable dye residue described in Japanese Patent No. 124337.

These dye-donating materials may be used alone or in combination of two or more. 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 types. Although it may be determined accordingly, the amount used can be, for example, 0.005 g to 50 g, preferably 0.1 g to Log.

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material using any method. Cresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.) and then neutralized with an acid (e.g., citric acid or nitric acid, etc.). or an aqueous solution of a suitable polymer (e.g. gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.)
It can be used after being dispersed using a ball mill.

Next, the photosensitive silver halide used in the present invention will be described. Any silver halide can be used, and examples thereof include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. The photosensitive silver halide can be prepared by any method commonly used in the photographic field, such as a single jet method.

In a preferred embodiment of the present invention, the photosensitive silver halide contained in the heat-developable photosensitive material has a silver iodide content of 0 mol% to 40 mol%, more preferably silver iodide. The content is 0.1 mol% to 4 mol%. Preferred silver halide in this case is silver iodobromide or silver chloroiodobromide. Preparation of such preferred silver halide includes
Any of the acid method, neutral method, ammonia method, etc. may be used, but the ammonia method is particularly suitable. Further, as a method for reacting the soluble root salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a back mixing method in which silver halide grains are formed in an excess of silver ions. As one of the simultaneous mixing methods, the Chondrald double jet method can be used, in which the pAg of the solution in the reaction vessel in which silver halide is produced is arbitrarily controlled, and the addition rate of the silver and halogen solutions is controlled. According to this method, a so-called monodisperse silver halide emulsion (described later) in which crystals and grain sizes on both sides of the silver halide grains are nearly uniform can be obtained.

In the present invention, as the photosensitive silver halide contained in the heat-developable photosensitive material, one having a core/shell structure can be used. That is, in a preferred embodiment of the present invention, core/shell type silver halide grains are used in which the grain has a multilayer structure in which the halogen composition is different on the surface and inside. In this case, a silver halide emulsion having grains in which the halogen composition changes stepwise or continuously can be used.

In addition, its shape is cubic, spherical, octahedral, dodecahedron,
It can be used whether it has a clear crystal habit such as a tetradecahedron or not. This type of silver halide is described in JP-A-60-215948.

More preferred core/shell type photosensitive silver halide grains used in the present invention are core/shell type photosensitive silver halide grains having a surface latent image type shell.

A core/shell type photosensitive silver halide emulsion which is more preferably used in the present invention can be produced by coating monodisperse photosensitive silver halide grains with a shell as a core.

In order to form the core into monodisperse silver halide grains, grains of a desired size can be obtained by a double jet method while keeping pAg constant. Furthermore, the method described in JP-A-54-48521 can be applied to silver halide emulsions containing highly monodisperse photosensitive silver halide. A preferred embodiment of the method is a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. It is manufactured by. At this time, by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc.
Silver halide emulsions containing silver halide grains for highly monodisperse cores can be obtained.

By sequentially growing shells using monodisperse core grains as described above according to the manufacturing method of a monodisperse emulsion, monodisperse core/shell type photosensitive silver halide containing monodisperse core/shell type photosensitive silver halide which is more preferably used in the present invention is produced. A silver halide emulsion can be obtained.

In the core/shell type photosensitive silver halide grains more preferably used in the present invention, the thickness of the shell covering the core is 0.05% to 0.05% of the silver halide grain size.
It is preferably 90%, more preferably in the range of 1% to 80%. In the silver halide composition of the core, the content of silver iodide is preferably from 0.1 mol% to 40 mol%. In the silver halide composition of the shell, the silver iodide content is preferably 0 mol % to 6 mol %. More preferably, it is a core/shell type silver halide in which the silver iodide content in the core is 2 mol % or more higher than the silver iodide content in the shell. Particularly preferably, the silver iodide content of the core is 2 mol %, the silver iodide content of the shell is 0%, and the volume ratio of the core to the shell is 1=1, so that the total silver iodide content is It is 1 mol%.

Further, the present invention includes, for example, JP-A-58-111933;
58-111934, 58-108526, Research Disclosure No. 22534, etc., each of these crystal planes has two parallel crystal planes, and each of these crystal planes is different from other units of this particle. It is also possible to use a silver halide emulsion containing tabular silver halide grains having a larger area than the crystals and an aspect ratio, that is, a ratio of grain diameter to thickness of 5:1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
．． 592.250, 3,206.313, 3,
No. 317,322, No. 3,511.622, No. 3.4
No. 47.927, No. 3.76L266, No. 3,703
, No. 584, No. 3,736.140, etc., and the internal latent image type silver halide grains whose surfaces are not fogged in advance are as described in the above-mentioned specifications.
These are silver halide grains in which the sensitivity inside the grain is higher than the sensitivity on the surface of the silver halide grain. Also, U.S. Patent No. 3
．． 271,157, 3,447,927 and 3,531,291, silver halide emulsions having silver halide grains containing polyvalent metal ions, or A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in U.S. Pat. -3852
Silver halide emulsions consisting of grains having a layered structure as described in publications such as No. 5, etc., and other JP-A-52-1566
14 and the silver halide emulsion described in JP-A-55-127549.

The photosensitive silver halide used in the present invention may be chemically sensitized by any method in the photographic field.

In a preferred embodiment of the present invention, the silver halide grains contained in the photothermographic material are gold-sensitized.

In that case, other chemical sensitization may be used in combination. Preferably,
Chemical sensitization is performed using a combination of sulfur sensitization and gold sensitizer.

The oxidation number of gold in the gold sensitizer used for gold sensitization is arbitrary and may be +1 or +3, and various gold compounds can be used. Typical examples of gold sensitizers include gold chloride W potassium chlorooleate, Olink trichloride,
Potassium auric thiocyanate, potassium iodo oleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, halogenation≦approximately 0.1 to 10 mg per mole
, preferably 1.5X10-' to 4.0xlO-'*
It is.

Any sulfur sensitizer can be used in combination with the gold sensitizer or used alone.

For example, thiosulfate, allylthiocarbamide thiourea,
Examples include allyl isothiocyanate, cystine, pt-luenethiosulfonate, and rhodanine. Other U.S. Patent No. 1,574,944, U.S. Patent No. 2.410,
No. 689, No. 2.278.947, No. 2,728
．． No. 668, No. 3.501, 313, No. 3.65
6.955 specifications, German Patent No. 1,422,86
No. 9, JP-A-56-24937, JP-A-55-450
Sulfur sensitizers described in Publication No. 16 and the like can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but as a guide, it is about 0.5 to 2.0 cm per mole of silver halide, Preferably 0.
It is 7 to 1.5 ■.

When a gold sensitizer and a sulfur sensitizer are used together, either of them may be added to the emulsion first, or they may be added at the same time.

The gold sensitizer is preferably gold chloride, and the sulfur sensitizer used in combination with the gold sensitizer is preferably a thiosulfur salt.

The silver halide grains used in the present invention may be coarse or fine, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm. It is 0.01 μm to 0.5 μm.

In the present invention, as another method for preparing photosensitive silver halide, a technique is used in which 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. You can also do that.

These photosensitive silver halide and photosensitive silver salt forming components are
They can be used in combination in various ways, and the amount used is preferably 0.001 g to 50 g, more preferably 0.1 g to 10 g, per layer and 1M of support.
It is.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holopolar cyanine,
Examples include various dyes such as styryl, hemicyanine, and oxonol.

The preferred amount of these sensitizing dyes to be added is lXl0- per mole of photosensitive silver halide or silver halide forming component.
'Mole - 1 mole. More preferably, lXl0-'
~I x 10-' mol.

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 that can be used in the heat-developable photosensitive material of the present invention include Japanese Patent Publication No. 43-4921, Japanese Patent Application Laid-Open No. 49-52
No. 626, No. 52-141222, No. 53-3622
4, US Pat. No. 53-37610, and US Pat. No. 53-37626, as well as specifications such as US Pat. Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver palmitate, as described in
Silver stearate, silver arachidonic acid, silver behenate, α-(
silver 1-phenyltetrazolethio) acetate, and silver aromatic carboxylates such as silver benzoate, silver phthalate, etc.
JP 44-26582, JP 45-12700, JP 45-18416, JP 45-22185, JP 5
2-137321, JP-A-58-118638, JP-A-58-118639, U.S. Pat. No. 4,123.
There is a silver salt of an imino group described in the specification of No. 274.

Other silver complex compounds with a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, and imizolithion as described in U.S. Pat. No. 4,168,980. Silver salt etc. are used.

Among the above organic silver salts, imino group silver salts are preferred;
Particularly preferred are silver salts of benzotriazole derivatives, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives.

The organic silver salts used in the present invention may be used alone or in combination of two or more. Alternatively, the silver salt may be prepared in a suitable binder and used as is without isolation.
The isolated product may be used after being dispersed in a binder by an appropriate means. Dispersion means include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like.

In addition, as a method for preparing organic silver salts, a method is generally used in which silver nitrate and raw materials are dissolved and mixed in water or an organic solvent, but if necessary, a binder may be added or hydroxylated. It is also effective to add an alkali such as sodium to promote dissolution of organic compounds, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is preferably 0.01 mol to 500 mol, more preferably 0.1 to 100 mol per 111 mol of photosensitive halogen. More preferably, it is 0.3 to 30 mol.

Reducing agent used in the photothermographic material of the present invention (reducing agent precursor is also included in the reducing agent herein)
Those commonly used in the field of heat-developable photosensitive materials can be used.

Examples of reducing agents that can be used in the present invention include U.S. Pat. Nos. 3,531,286 and 3,761,27
No. 0, the specifications of No. 3,764,328, and RD
(Research Disclosure) Kan 12146, Circular 15108, N115127 and JP-A-56-27
No. 132, U.S. Patent No. 3,342,599, U.S. Patent No. 3,719,492, JP-A-53-1356
p- described in each publication such as No. 28, No. 57 to 79035, etc.
Phenyl diamine type and p-aminophenol type developing agents, phosphoramidophenol type, sulfonamide aniline type developing agents, hydrazone type color developing agents and their precursors, or phenols, sulfonamide phenols, or polyhydroxybenzenes. , naphthols, hydroxybinaphthyls and methylene bisnaphthols, methylene bisphenols, ascorbic acid, 3-pyrazolidones, and pyrazolones can be used.

As a particularly preferable reducing agent, JP-A-56-146133
N-(p-N
.

N-dialkyl) phenylsulfamate can be mentioned.

Two or more types of the above-mentioned reducing agents may be used simultaneously.

The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide used, the type of organic acid silver salt, the type of other additives, etc., and is not necessarily constant. However, the amount is usually preferably from 0.01 to 1,500 mol, more preferably from 0.1 to 200 mol, per mol of photosensitive silver halide.

Binders that can be used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate,
These include synthetic or natural polymeric substances such as ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose Pi, protein, starch, and gum arabic. One or more of these can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably to use a mixed binder of gelatin and polyvinylpyrrolidone described in JP-A-59-229556. That's true.

The preferred amount of binder used is usually 0.05 g to 50 g per m' of support, more preferably 0.1 g.
g to 10 g.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use 10 g to 10 g, more preferably 0.0 g to 10 g.
It is 25g to 4g.

The heat-developable photosensitive material of the present invention can be obtained by forming a photographic constituent layer on a support, and examples of the support that can be used here include polyethylene film, cellulose acetate film, polyethylene terephthalate film, etc. Synthetic plastic films such as polyvinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper, and resin coated paper, and electron beam curable resin compositions coated and cured on these supports. Examples include supports.

When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, it is preferable that various thermal solvents are added to the photothermographic material and/or the image receiving member. A thermal solvent is a compound that promotes thermal development and/or thermal transfer. Examples of these compounds include, for example, U.S. Pat. No. 3,347,675, U.S. Pat.
RD (Research Disclosure + -) Na 17
643 (X II), JP-A-59-229556, JP-A No. 59-68730, JP-A No. 59-84236, JP-A No. 6
No. 0-191251, No. 60-232547, No. 60
-14241, No. 61-52643, Japanese Patent Application No. 60-218768, No. 60-181965, No. 6
No. 0-184637, etc., U.S. Patent No. 3.438.776
No. 3.666477, 3.667, 959 specifications, JP-A-51-19525, JP-A-53-2482
9, No. 53-60223, No. 58-118640, and No. 58-198038, examples of which are particularly useful in carrying out the present invention include: , for example, urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, p-toluamide, p-butoxybenzamide, etc.), sulfonamide derivatives (e.g., benzenesulfonamide, α-toluene, etc.). sulfonamide, etc.), polyhydric alcohols (for example, 1.5-bentanediol, 1.6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycols.

As the above-mentioned thermal solvent, a water-insoluble solid thermal solvent is more preferably used. Here, the water-insoluble solid thermal solvent is solid at room temperature, but at high temperatures (60°C or higher, preferably 100°C or higher).
It is a compound that becomes liquid at temperatures above 130°C or higher and 250°C or lower, and has an inorganic/organic ratio (“Organic Conceptual Diagram” by Yoshio Koda, Sankyo Publishing ■, 1984) of 0.5 to
3.01 preferably 0.7 to 2.5, particularly preferably 1
．． Refers to compounds in the range of 0 to 2.0.

Specific examples of the above-mentioned water-soluble heat solvent include, for example,
It is described in No.-278331 and No. 60-280824.

Examples of the layer to which a heat solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member, etc., and the heat solvent is added to each layer so as to obtain an effect depending on each layer.

The preferred amount of the heat solvent added is usually 10% to 500% by weight, more preferably 30% to 200% by weight of the binder amount.
Weight%.

The photothermographic material of the present invention may contain various additives in addition to the above-mentioned components, if necessary.

A color toning agent known in the heat-developable light-sensitive material may be added to the heat-developable light-sensitive material as a development accelerator in combination with the cyclic compound of the present invention. As a color toning agent, for example, JP-A No. 46-4928 and JP-A No. 46-607
No. 7, No. 49-5019, No. 50-2524, No. 5
No. 0-67132, No. 50-67641, No. 50-1
No. 14217, No. 52-33722, No. 52-998
No. 13, No. 53-1020, No. 53-55115,
No. 53-76020, No. 53-125014, No. 5
No. 4-156523, No. 54-1565324, No. 5
No. 4-156525, No. 54-156526, No. 55
-4060, 55-4061, 55-3201
No. 5, as well as West German Patent Nos. 2,140,406, 2,141.063, 2,220,618, US Pat. No. 3.847.612, and West German Patent No. 3.782.
941, 4゜201.582, etc., as well as JP-A-57-207244 and JP-A-57-2072.
No. 45, No. 58-1896328, No. 58-1935
There are compounds described in various publications such as No. 41.

Other development accelerators include compounds described in JP-A-59-177550 and JP-A-59-111636.

Further, development accelerator releasing compounds described in Japanese Patent Application No. 59-280881 can also be used.

As an antifoggant, for example, U.S. Patent No. 3.64゜5
．． Higher fatty acids described in the specification of No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983,
N-halogen compounds described in Publication No. 1-47419, U.S. Pat.
Mercapto compound-releasing compounds described in Japanese Patent No. 0725, arylsulfonic acids described in Japanese Patent No. 49-125016, lithium carboxylate salts described in Japanese Patent No. 51-47419, British Patent No. 1.455,271 ,
Oxidizing agents described in JP-A-50-101.019, sulfinic acids or thiouracils described in JP-A-53-19825, JP-A-51-81124, JP-A-55-9
Disulfide and polysulfide compounds described in Publication No. 3149, rosin or diterpenes described in Publication No. 51-57435, polymer acids having free carboxyl groups or sulfonic acid groups described in Publication No. 51-104338, and US Pat. 4.138.265, and 1.1 described in JP-A-54-51821 and U.S. Pat. No. 4.137,079.
2.4-) Riazole or 5-mercapto-1,2
, 4-triazole, 1.2.3.4-thiatriazoles described in JP-A-55-142331, JP-A-55-142331;
-46641, 59-57233, 59-57
Dihalogen compounds or trihalogen compounds described in JP-A No. 234, 100-ol compounds described in JP-A No. 59-111636, hydroquinone derivatives described in JP-A No. 60-198540, and hydroquinone derivatives described in JP-A No. 60-227255. and benzotriazole derivatives.

Further particularly preferred anti-capri agents include the hydrophilic group-containing inhibitors described in Japanese Patent Application No. 60-218169, the polymer inhibitors described in Japanese Patent Application No. 60-262177, and the Examples include the inhibitor compound having a ballast group described in No. 60-263564.

Furthermore, inorganic or organic bases or chlorine group precursors can be added. Examples of base precursors include compounds that decarbonize by heating and release basic substances (e.g. guanidinium trichloroacetate), compounds that decompose by reactions such as intramolecular nucleation substitution reactions and release amines, etc. For example, JP-A-56-130745
No. 56-132332, British Patent No. 2,079
, 480, U.S. Patent No. 4,060°420,
JP 59-157637, JP 59-166943, JP 59-180537, JP 59-174830,
Examples include base releasing agents described in Japanese Patent No. 59-195237 and the like.

In addition, various additives used in heat-developable photosensitive materials as necessary, such as antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, spreading agents, capping agents, and surfactants. , anti-fading agents, etc., specifically RD (
Research Disclosure) Magazine Vol.1.170.1
June 978 Uo No. 17029, patent application 1986-27661
It is described in No. 5, etc.

The heat-developable photosensitive material of the present invention contains (a) photosensitive silver halide, (b) a reducing agent, and (c) a binder.

When used as a color light-sensitive material, it contains (d) a dye-providing substance. Furthermore, it is preferable to contain (e)) organic silver as necessary. Basically, these may be contained in one heat-developable photosensitive layer, but they do not necessarily need to be contained in a single photographic constituent layer. For example, if the heat-developable photosensitive layer is divided into two layers, The components a), (b), (c), and (e) are contained in one heat-developable photosensitive layer, and the dye-providing substance (d) is contained in the other layer adjacent to this photosensitive layer. They may be contained in two or more constituent layers as long as they are in a state where they can react with each other.

Further, the heat-developable photosensitive layer may be divided into two or more layers: a low-sensitivity layer and a high-sensitivity layer, a high-density layer and a low-density layer, or more.

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers. In the case of full-color photosensitive materials,
Generally, it has three heat-developable photosensitive layers with different color sensitivities, and in each photosensitive layer, dyes with different hues are formed or released by heat development.

Usually, a yellow dye is combined in the blue-sensitive layer, a magenta dye in the green-light-sensitive layer, and a cyan dye in the red-sensitive layer, but the combination is not limited thereto. It is also possible to combine a near-infrared sensitive layer.

The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on a support, or a blue-sensitive layer is sequentially formed on a support. , a green-sensitive layer, a red-sensitive layer, or a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer sequentially on the support.

In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer.

To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

The heat-developable photosensitive material of the present invention usually preferably has a
0°C to 200°C, more preferably 100°C to 170°C
Developing can be carried out simply by heating within a temperature range of, preferably 1 second to 180 seconds, more preferably 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development. Alternatively, the transfer may be carried out by supplying water and then applying heat if necessary. Moreover, you may perform preheating in the temperature range of 70 degreeC - 180 degreeC before exposure. In addition, as described in Japanese Patent Application Laid-Open No. 60-143338 and Japanese Patent Application No. 60-3644, in order to improve mutual adhesion, the photosensitive material and image receiving member are heated at 80°C to 250°C immediately before thermal development transfer. Each may be preheated at different temperatures.

Various heating means can be used for the heat-developable photosensitive material of the present invention.

As the heating means, all methods that can be applied to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, or passing through a high temperature atmosphere. Alternatively, high-frequency heating may be used, or furthermore, a conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer, and the Joule heat generated by energization may be utilized. You can also. There are no particular restrictions on the heating pattern, including preheating and then reheating, high temperature for a short time, low temperature for a long time, continuous rise, continuous fall, or both. Although repeated or even discontinuous heating is possible, a simple pattern is preferable, and a method in which exposure and heating proceed simultaneously may also be used.

When the present invention is applied to a transfer type photothermographic material, an image receiving member is provided as described above. The image-receiving layer of the image-receiving member that can be effectively used in that case may have the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, such as a tertiary amine or quaternary ammonium salt. Among the polymers described in U.S. Pat. No. 3,709,690 are preferably used. A typical image-receiving layer for diffusion transfer is obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. Another useful dye-receiving material is JP-A-57-20
The glass transition temperature described in Publication No. 7250 etc. is 40℃
The above examples include those formed of heat-resistant organic polymer substances of 250° C. or lower.

These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support.

Examples of the heat-resistant polymer substances include polystyrene, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl. Polyacetals such as butyral, polyvinyl chloride, chlorinated polyethylene, polytrichloride fluorinated ethylene, polyacrylonitrile, poly-N.

N-dimethylallylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl Polyesters such as methacrylate, poly-ter-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate,
Examples include polysulfone, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also,
"Polymer Handbook, Second Edition" (
Edited by Joy Brandrup and E.H. Inmargat) John Willian and Sands Publishing (Polym
erHandbook 2nd ed, (J, Bran
drup, E., H., Iwmergut & I) John
Also useful are synthetic polymers having a glass transition temperature of 540°C or higher, as described in Wiley & 5ons). Generally, the molecular weight of the polymer substance is 2.000~
200,000 is useful. These polymeric substances are
It may be used alone or in a blend of two or more types, or two or more types may be used in combination.
A combination of two or more types may be used as a power supply combination.

A particularly preferable image-receiving layer is JP-A-59-22342
Examples include a layer made of polyvinyl chloride described in Japanese Patent Application No. 5, and a layer made of polycarbonate and a plasticizer described in JP-A-60-19138.

These polymers can also be used as a support and an image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or from multiple layers. good.

As the support for the image receiving member, any material such as a transparent support or an opaque support may be used, but for example, films of polyethylene glycol, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, etc., and films of these materials may be used. Supports containing pigments such as titanium oxygen, barium sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments on paper, fabrics, glasses, metals such as aluminum, supports on which electron beam-curable resin structures containing pigments are coated and cured, and coated layers containing pigments are provided on these supports. Examples include supports such as Furthermore, the cast coat described in Japanese Patent Application No. 61-126972 is also useful as a support.

In addition, a support with a pigment-containing electron beam curable resin composition coated and cured on paper, or a support with a pigment coating layer on paper and an electron beam curable resin composition on the pigment coating layer. The resin layer of the support coated with and cured can be used as an image-receiving layer, so it can be used as is as an image-receiving member.

The heat-developable photosensitive material of the present invention is disclosed in RD (Research Disclosure) No. 15108, JP-A-57-198458.
The material may be a so-called monotone photothermographic material in which a photosensitive layer and an image-receiving layer are formed on the same support, as described in Japanese Patent No. 57-207250 and Japanese Patent No. 61-80148.

The heat-developable photosensitive material of the present invention is preferably provided with a protective layer.

Various additives used in the photographic field can be used in the protective layer. The additives include various capping agents, colloidal silica, slipping agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers,
Low-boiling organic solvents, antioxidants, hydroquinone derivatives,
Examples include polymer latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), silver salt particles, and non-photosensitive silver halide particles.

Regarding these additives, please refer to RD (Research Disclosure) Vol. 170. June 1978 Fish 17
No. 029 and Japanese Patent Application No. 60-276615.

〔Example〕

Hereinafter, specific examples of the present invention will be described. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 In this example, a core/shell type silver iodobromide emulsion, an organic silver salt dispersion, a dye-providing substance dispersion, and a reducing agent dispersion were prepared as follows, and these were used to heat the A sample m 1-11hlO of a photosensitive material for development was prepared. Further, in this example, the present invention was applied to a transfer type heat-developable photosensitive material, so the preparation of the image receiving member will also be explained below.

■Preparation of core/shell type silver iodobromide emulsion Silver iodobromide content 1 mol%, average grain size 0.3. A core/shell type emulsion E m-1 of um was prepared by the following method.

At 40°C, JP-A-57-92523, JP-A-57-92523;
20 g of ossein gelatin, 0.2 mol of ammonia and a silver iodobromide seed emulsion (average grain size 0.1 μm, silver iodide content 2 mol%
) 0.0385-T-Ruwo dissolved Lf water? 8i (A)
Potassium iodide 0.04 mol/l and potassium bromide 1.94 mol/i in 1000 tml! Aqueous solution B-1 containing 1 mole of silver nitrate and 500 m6 of solution C, which is an aqueous solution containing 2 moles of ammonia, were simultaneously added at the maximum allowable rate without generating small particles while keeping the pAg constant. A core part was prepared. At this stage, it was confirmed that each emulsion was monodispersed. After the addition of liquid B-1 was completed, liquid B-2 containing 1.98 mol/l of potassium bromide was added together with liquid C to form a shell. The pH during the addition was 9.0. pAg was kept at 9.8. pHSpAg was controlled with a 50% acetic acid aqueous solution and a 25% potassium bromide aqueous solution, respectively. In this way, the grain shape is regular octahedral, the average grain size is 0.31℃m, the grain size distribution is 13%, and the silver iodide content is 2 mol% in the core part, 0 mol% in the shell part, and the overall average core with a shell thickness of 0.031 μm/
A shell-type silver halide emulsion Em-1 was produced.

This emulsion Em-1 was washed with water and desalted, an aqueous ossein gelatin solution (containing 30 g of gelatin) was added, and after separation, the volume was adjusted to 800 ml with distilled water.

■Preparation of silver salt dispersion-1 8g of 5-methylbenzotriazole silver 2B obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent and poly(N-vinylpyrrolidone) 16.0 g and 1.33 g of 4-sulfobenzotriazole sodium salt were dispersed in an alumina ball mill, adjusted to pH 5.5, and adjusted to 200 va 12.

■Preparation of photosensitive silver halide dispersion The silver halide emulsion Em-t prepared above was subjected to chemical sensitization and spectral sensitization using the following sensitizers to give red, green, and blue sensitization halogen sensitization. A silver oxide emulsion dispersion was prepared.

(a) Preparation of red-sensitive silver iodobromide emulsion The above silver halide emulsion Em=1 was added to 200 m1! Sodium thiosulfate 3. On+gChloroauric acid 0.4rmgAmmonium thiocyanate 10mgThe following sensitizing dye (a)
Methanol 1%? liquid
12 ml Sensitizing dye (a) (b) Preparation of green-sensitive silver iodobromide emulsion 200 m7 of the above silver halide emulsion Em-1! Sodium thiosulfate 4.0mg Chlorauric acid 0.4mg Ammonium thiocyanate Omg Sensitizing dye below (b) 1% methanol solution 12++1 sensitizing dye (b) (c) Preparation of blue-sensitive silver iodobromide emulsion The above halogenation Silver emulsion Em-1 200++1 Sodium thiosulfate 3.0 mg Chloroauric acid 0.4 mg Ammonium thiocyanate 10 mg The following sensitizing dye (c) 1% methanol solution 12n/sensitizing dye (c) ■ Dye-donor dispersion = Preparation of 1 35.5 g of the following dye-providing substance (1), 5.0 g of the following hydroquinone compound, and the following antifoggant were dissolved in ethyl acetate 200+11, and Alkanol Gelatin (Rouslow, type 17819P C
) It was mixed with 720 nl of an aqueous gelatin solution containing 30.5 g, dispersed using an ultrasonic homogenizer, and after distilling off ethyl acetate, the volume was adjusted to p85.5 and the volume was 795 ml.

Dye-donor substance (1) (magenta dye-donor substance) (,H) x: 40% by weight y: 60% by weight Hydroquinone compound h ■Preparation of reducing agent dispersion-1 23.3 g of the following reducing agent, the following development accelerator 1 .10 g,
Dissolve 14.6 g of poly(N-vinylpyrrolidone) and 0.50 g of the following fluorosurfactant in water, and adjust the pH to 5.5.
25On+j+.

Reducing agent development accelerator C/H2-c-H Su〇H2 Surfactant Na03S -CIl COCooCHz (CFz
CFz)C82C00CHz(CFzCFz)nH(m
+n.2 or 3) (1) Preparation of heat-developable photosensitive material-1 A sample of the heat-developable photosensitive material was prepared as follows. That is, 12° fm of organic silver salt dispersion-1 prepared above! , 10 nl of the green-sensitive silver halide emulsion (using the above emulsion 8 m-1), 2.0 g of gelatin, and dye-providing substance dispersion-1.
39.8 mg of 12.5 m# of reducing agent dispersion-1 and the cyclic compound of the present invention or comparative compound A (
The amount added is shown in Table 1), and then a hardener solvent [
Tetra(vinylsulfonylmethyl)methane and taurine are reacted at a ratio of 1:1 (weight ratio) and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin so that the amount of tetra(vinylsulfonylmethyl)methane is 3% by weight. . - After adding 3.80 g of polyethylene glycol 300 (manufactured by Kanto Kagaku Co., Ltd.) using heat as an 8 agent, the amount of silver was is 1.76g/m”
A protective layer consisting of a mixture of the phenylcarbamoylated gelatin and poly(N-vinylpyrrolidone) was further applied on top of the sample 11m shown in Table 1.
Photothermographic materials Nos. 1 to 10 were prepared.

■Preparation of image receiving member-1 Polyvinyl chloride (n=1.10
0, Wako Pure Chemical Industries, Ltd.) in tetrahydrofuran was applied so that the amount of polyvinyl chloride was 12 g/m''.

The photothermographic material is exposed to light through a step wedge, and combined with the image receiving member, ? Development m <150 with developer module 277.3M (manufactured by M)
After heat development was carried out for 1 minute at .degree. C., the photothermographic material and the image receiving member were immediately peeled off, and a magenta step wedge negative image was obtained on the polyvinyl chloride surface of the image receiving member.

Table 1 shows the maximum density, sensitivity, and capri density of the magenta transfer image obtained by thermal development in relative values.

Sensitivity was determined as a point of Capri +0.2, and expressed as a relative value with the sensitivity of comparison sample No. 1 as 100.

As understood from Table 1, samples 11h2 to 9 of the present invention
Comparatively superior in terms of sensitivity, maximum concentration, and capri, compared to a comparative sample that does not use the cyclic compound of the present invention.

Table 1 fL comparison (, \'IA) Example-2 Example-1 except that the composition of the dye-providing substance dispersion in Example-1 was changed to the dye-providing substance dispersion a''-c shown below.
A coating solution having the same coating composition for the photosensitive layer as Samples 11 & L1 and No. 2 was coated on the same polyethylene terephthalate film as in Example-1 in the same manner as in Example-1, and dried to obtain heat-developable photosensitive material samples Na11 to 16. It was created. The dye-providing substance dispersion liquid and the type of dye-providing substance used in each sample are shown in Table-2.

Dye-donor dispersion liquid a> The dye-donor substance in the dye-donor dispersion liquid is the following dye-donor substance!
(2) Example except that (added it 83g)
The same dye-providing substance dispersion as in 1.

Dye-providing substance (2) (yellow dye-providing substance) <Dye-providing substance dispersion b> Dye-providing substance (3) below (addition amount 90 g
) was the same dye-providing substance dispersion as in Example-1 except that it was changed to

Dye-providing substance (3) (cyan dye-providing substance) Dye-providing substance dispersion C> Dye-providing substance (4) (addition amount 123
The same dye-providing substance dispersion as in Example-1 except that g) was changed.

Dye-providing substance (4) x: 50% by weight y: 50% by weight Photosensitive material samples N1111 to 16 were subjected to the same exposure and heat development as in Example-1. Obtained transferred image (sample 1'
hll~16) was subjected to the same image evaluation as in Example-1. The results are shown in Table-2.

Table 2 Below margin Example-3 The dye-providing substance dispersion was replaced with the dye-providing substance dispersion described in Example-2 on a 180 μm thick photographic transparent polyester terephthalate film having an undercoat layer. A photosensitive layer coating solution having the same composition as Sample 11h2 of Example-1 except that the silver halide emulsion was changed to the red-sensitive silver iodobromide described in Example-1 was applied to a wet film thickness of 70 μm and dried. 1 A light layer was applied.

A first intermediate layer having the following composition was coated on the first photosensitive layer.

Gelatin 0.65/I@”
Polyvinylpyrrolidone 0.343/m2
The following compound 0.2Vm"Methylbenztriazole silver 0.6θ/m2p-butoxybenzamide 1.OB/m"2.4-dichloro-6-hydroxy-8-triazine sodium 20mg/rn
2H3 A photosensitive layer coating solution having the same composition as Sample Magnet 2 of Example-1 was coated on the first intermediate layer to a wet film thickness of 50 μm to form a second photosensitive layer.

A second intermediate layer having the composition of the first intermediate layer with the following yellow filter dye (0.2 g/m'') added was coated on the second photosensitive layer.

Yellow filter dye CH3 ■ Further, on the second intermediate layer, a dye-providing substance dispersion was applied to the Example-
Sample Na2 had the same composition as Sample Na2 in Example-1, except that the dye-providing substance dispersion a described in Example 2 was changed to dye-providing substance dispersion a, and the silver halide emulsion was changed to blue-sensitive silver iodobromide described in Sample Ni12 in Example-1. A photosensitive layer coating solution was applied to a wet film thickness of 80 μm and dried to form a third photosensitive layer.

Furthermore, a protective layer having the following composition was coated on the third photosensitive layer to obtain a multilayer photosensitive material (Sample Fish 17).

Gelatin 0.28g/m" Polyvinylpyrrolidone 0.14g/m"S
i O2O, 36g/m” Saffron 1.0 g/m2p
-Butoxybenzamide 0.42 g/m'' The obtained photosensitive material sample N117 was exposed to red light, green light and blue light of 800 CMS through a step wedge, and heat development was performed in the same manner as in Example-1. Transfer density of the obtained cyan, magenta and yellow dyes (D
max, Dmin) were measured.

The results are shown in Table-3.

The following margin is ゛゛1″,,゛’;゛.

Table-3 ・I・′　　.

ζ/ [Effects of the Invention] As described above, the heat-developable photosensitive material of the present invention has the advantage of good developability, high sensitivity, and small capri during development.

Claims (1)

[Claims] 1. In a heat-developable photosensitive material containing a photosensitive silver halide, a reducing agent, and a binder, an oxygen atom, -NR_1- (R_1 is a hydrogen atom or an alkyl group), -CONH-, ▲mathematical formula There are , chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
It has at least one group selected from the group consisting of (R_2 is a hydrogen atom or an alkyl group) and -NHCONH-, and has at least two sulfur atoms and a carbon chain as essential ring constituent components, and the group and the A photothermographic material characterized in that at least one of the photographic constituent layers contains a cyclic compound in which each sulfur atom is bonded through the carbon chain.