JPS6265035A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the lowering of the sensitivity and maximum density as well as to inhibit thermal fogging by using a specified compound as an anti-foggant. CONSTITUTION:A compound represented by the formula (where X is a residue off a development retarder, L is a bivalent group and R is hydroxyl, carboxyl, sulfo, sulfinic acid or a salt thereof) as an anti-foggant is incorporated into a photosensitive element consisting essentially of photosensitive silver halide, an org. silver salt, a reducing agent and a binder on a support. It is preferable that the compound represented by the formula has -SH as X in the formula. It is especially preferable that the compound has a heterocyclic residue contg. N as X and sulfo or a salt thereof as R. The compound represented by the formula may be incorporated into any of the constituent layers of a photosensitive material but is preferably incorporated into the photosensitive layer. The anti-foggant lowers the minimum density without lowering the maximum density, can produce a significant anti-fogging effect and keeps the sensitivity high. The anti-foggant is suitable for any of monochromatic and color photosensitive materials.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-developable photosensitive material that forms an image by heat development, and specifically relates to fog in heat development (thermal fog).
The present invention relates to a heat-developable photosensitive material with improved properties.

[Background of the Invention] In contrast to ordinary wet-type silver halide photosensitive materials that require wet processing using a developing solution, etc., heat-developable photosensitive materials, in which an image is obtained by dry processing such as heating after image exposure, are It has many advantages in terms of time, cost, and concerns about pollution.

Regarding such heat-developable photosensitive materials, many proposals have been made not only for monochrome use but also for heat-developable color photosensitive materials. No. 198458,
No. 57-207250, No. 58-40551, No. 5
No. 8-58543, No. 58-79247, and No. 59-
No. 12431, No. 59-22049, No. 59-687
No. 30, No. 59-124339, No. 59-124
No. 333, No. 59-124331, No. 59-1591
No. 59, No. 59-181345, No. 59-15916
No. 1, No. 58-116537, No. 58-123533
No. 58-149046, No. 58-14947, etc.

The basic structure of the heat-developable color photosensitive materials proposed in these proposals consists of a photosensitive element and a receiving element. It consists of a donor substance and a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense. In this heat-developable photosensitive material,
Optical information is imparted to the photosensitive silver halide by image exposure, and acts on the photosensitive silver halide during thermal development.
Alternatively, the developer that has not acted reacts with the dye-providing substance, thereby releasing or forming an image-forming dye.

The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image.

However, regardless of monochrome or color, the highest i
l! If an attempt is made to obtain an image with sufficiently high density, the disadvantage is that the minimum density fog (thermal fog) becomes large. This thermal fog phenomenon is thought to be due to the generation of fog nuclei on the surface of photosensitive silver halide or organic silver salt during thermal development, but the detailed mechanism is not clear.

On the other hand, many of the compounds that are said to be effective as fog suppressants in photosensitive materials that do not use organic silver salts have no fog suppressing effect or have the opposite effect in photothermographic materials that contain organic silver salts. Many of them have drawbacks such as increased fog or a decrease in sensitivity, and no effective findings as thermal fog suppressants have been provided.

For example, JP-A-59-177550 discloses some antifoggants (development inhibitors) used in ordinary silver halide photographic light-sensitive materials (hereinafter also referred to as conventional light-sensitive materials). There is also a description of H in which the compound acts as a development accelerator in a heat-developable photosensitive material.

In response, various thermal antifoggants (hereinafter also referred to as development inhibitors) for use in heat-developable photosensitive materials have been proposed. For example, the mercury compound of U.S. Pat. No. 3.589.903, the N-halogen compound of U.S. Pat. No. 2.402.161, the peroxide of U.S. Pat.
617,907 Sulfur Compounds, U.S. Patent No. 4,10
2.312 palladium compound, Japanese Patent Publication No. 53-284
Sulfinic acids No. 17, Research Disclosure No. 469077, Mercaptotriazole No. 169079, U.S. Patent No. 4.137.079-1
．． Examples include 2,4-triazole.

However, these thermal antifoggants are either extremely harmful to the human body or have little antifogging effect, and the reality is that no satisfactory thermal antifoggant has yet been found.

[Objective of the Invention] Therefore, the object of the present invention is to provide a heat-developable photosensitive material with extremely small thermal fog and no decrease in sensitivity and high density polishing.
It is about providing.

[Structure of the Invention] The above-mentioned 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 binder on a support. This is achieved by a thermophenomenal photosensitive material containing a compound represented by formula (1).

General formula (1) In the formula, X represents a development inhibitor residue, L represents a bipolar group, and R represents a hydroxyl group, a carboxyl group, or its I3! , sulfo group or its salt, sulfine 7%91
Or it represents the salt.

[Specific Structure of the Invention] In the general formula (1), the development inhibitor residue represented by
Photographic Society of Japan, Cancer, Corona Publishing), page 354, Chemistry of Photography (written by Akira Sasai, published by Shashin Kogyo Publishing), pages 168-169, or The Theory of the Photographic Process (edited by T. H. James) , Macmillan) 3
In convection white light-sensitive materials such as those described on pages 96 to 399, residues of organic compounds known as development inhibitors (or antifoggants) may be used, preferably in water at 25°C. The organic compound has a silver salt solubility V4 (pKSI) of 10 or more.

A preferred example of the case where the residue of X in the general formula (1) is a compound represented by XH is shown in the following general formula (%).In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or an aryl group.

General formula (3) In the formula, R4 represents an atom, an alkyl group, or an aryl group (water), and R5 represents a hydrogen atom, an alkyl group, an aryl group, or a nitro group. n represents 1 or 2.

General formula (5) In the formula, R7 represents a hydrogen atom, an alkyl group or an aryl group.

General formula (6) In the formula, R8 represents a hydrogen atom, an alkyl group or an aryl group, and Y represents -N-1-〇- or -8-.

General formula (7) In the formula, R9 and Rho each represent a hydrogen atom, an alkyl group or an aryl group. However, R9 and Rho may combine to form a 5- to 6-membered ring.

R+1 is a thiol group or -NH-R+2 (R+2 represents a hydrogen atom, an alkyl group, or an aryl group ()-CH
- does not represent.

I2 In the formula, R13 represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group.

General formula (9) In the formula, RI4, R+s and R+s each represent a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a thioalkoxy group, a thiol group or a hydroxyl group.

General formula (10) In the formula, R17, R+s, R+9, R20 and R21 are each a hydrogen atom, an alkyl group, an aryl group, -NH
-R22 group (R22 represents a hydrogen atom, an alkyl group or an aryl group), a thiol group, an alkylthio group, a hydroxy group or an alkoxy group;

General formula (11) In the formula, R23 and R24 each represent a hydrogen atom or an alkyl group.

General formula (12) In the formula, R25 represents a hydrogen atom, an amine group, an alkyl group, or an aryl group, and Y is 10-1-S- or -N-
(R26 represents a hydrogen atom or amino) 1 or (2G represents an alkyl group).

General formula (13) In the formula, R27 and R28 each represent a hydrogen atom, an acyl group, an alkyl group, or an aryl group, and Y represents -C- or -N- (R29 represents a hydrogen atom or an alkyl group). Mouse.) However, R2q and R2 combine to form 5~
6 may form a negative ring.

General formula (14) In the formula, R3o1R3+ and R32 each represent a hydrogen atom, an alkyl group, or an aryl group. However, R30
and R3t may be combined to form a 5- to 6-membered ring. △
ne represents a counter anion.

In general formulas (2) to (14), preferably)71-
It is a compound having a nitrogen-containing heterocycle having a group, and more preferably a compound represented by the general formula (3).

In the general formula (1), L represents a divalent group,
L is preferably a divalent group represented by the following general formula (15).

General formula (15) % formula %) In the formula, Ll is an alkylene group having 1 to 7 carbon atoms (for example, methylene group, ethylene group, propylene group, etc.), arylene group (for example, p-phenylene group, m-phenylene group, etc.).
(0-phenylene group, etc.), imino group, carbonyl group, sulfonyl group, ether group, or a combination of these groups (
For example, alkylenecarbonylamino group, aralkyleneamino group, sulfonylamino group, etc.), and n represents O or 1.

In the general formula (1), R represents a hydroxyl group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a sulfinic acid group or a salt thereof.

The compound according to the present invention represented by the general formula (1) is:
It is preferably represented by the following general formula (16).

General formula (16) In the formula, Ll and n have the same meanings as Ll and n defined in the above general formula (15), and R has the same meaning as R as defined in the above general formula (1).

A more preferred compound of the present invention represented by the general formula (16) is a compound in which 4 L + 5 RN is substituted at the para position of the phenyl group.

Hereinafter, the compound of the present invention represented by the general formula (1) (
Hereinafter, representative examples of compounds of the present invention) will be shown, and the compounds of the present invention may have Pa 'i :h3
(P T”rt fi 11.

Core / 1 A size (5) 5H (11) [1z) (13] (1+) Eyes (1!1″) (Ig) (z3) (Z5) (z6) ■ (2y) (32n Compounds of the invention may be used, for example, in British Patent No. 1,275,70
No. 1, U.S. Patent No. 3,266.897, Japanese Unexamined Patent Publication No. 1983-
No. 89034, No. 53-28426, No. 55-210
It can be synthesized by referring to the method described in No. 67, No. 56-111846, etc.

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

The amount of the compound of the present invention added varies depending on conditions such as the type, amount, and mixing ratio of the photosensitive silver halide and organic silver salt used, but is approximately 1 mol per mol of photosensitive silver halide.
Preferably 0-6 to 10-1 mol, more preferably 10
-5 to 10-2 moles.

The compound of the present invention may be added to any of the constituent layers of the heat-developable photosensitive material (or may be added to one or more layers, but it may be added to the photosensitive layer containing photosensitive silver halide). In this case, the timing of addition of the compound of the present invention is from after the precipitation of the photosensitive silver halide grains used in the photosensitive layer is formed after physical ripening. The addition may be carried out at any time before the emulsion is coated, and any method commonly used for adding compounds can be applied; for example, the compound of the present invention may be added in the form of an acid or salt to water or It can be dissolved in an organic solvent such as methanol or a mixed solvent thereof and added to the emulsion.Also, if it can be dissolved in an organic solvent such as ethyl acetate or cyclohexane, it can be added to the emulsion after being made into an emulsion. You can also.

The heat-developable photosensitive material of the present invention contains photosensitive silver halide.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
A light-sensitive silver halide emulsion containing light-sensitive silver halide, which can be prepared by any method in the photographic technology field such as a single-jet method or a double-jet method, and which is prepared according to 11 production methods for ordinary silver halide gelatin emulsions. can be used arbitrarily.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include
Various methods include gold coral sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, 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. 0.01 μl to about 0.5 μl.

The photosensitive silver halide emulsion prepared by W as described above can most preferably be applied to the heat-transformable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

In the present invention, as another method for preparing 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 m salt. You can also do that. The photosensitive t&salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M is an H atom, NH+
1 or a metal atom, X represents C2, 3r or I, n represents 1 when M is an H atom or an NH4 group, and represents its valence when M is a metal atom. Metal atoms include lithium, sodium, potassium, rubidium, cesium,
Copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, Examples include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes such as K2 Pt C4
! s, 2Pt3rs, HAuC1+.

(NH4)2 1r Cff1s (NH4)31r
Cff1s.

(NH4)2 Ru C16,<NH4)3 Rtl
C16゜(NH4)2 R11Cff1s, (NH+
)3 Rh 3rs etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethyl Quaternary 7-piece sulfonium halides such as phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylbuazolium bromide, etc.), halogenated hydrocarbons (e.g.
Iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane W), N-halogen compound (N!
Rorosuccinimide, N-bromosuccinimide, N-
Bromophthalimide, N-bromoacetamide, N-
iodosuccinimide, N-, bromophthalazinone, N
-chlorophthalazinone, N-bromoacetanilide, N
, N-dibromobenzenesulfonamide, N-bromo-
N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) ) etc. can be given.

These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount used is preferably 0.001Q to 50g per 1f per layer, more preferably, 0.1 g to 10 g.

The photosensitive silver halide used in the heat-developable photosensitive material of the present invention preferably has a silver iodide content of 0 mol % to 40 mol %.
It is mole%.

More preferred photosensitive silver halide is a core/shell type having a surface latent image type shell.

When silver iodide is contained as the photosensitive silver halide, there are no particular restrictions on other halogen components of the photosensitive silver halide containing silver iodide, but preferred halogen components include silver iodobromide and Silver chloroiodobromide.

゛ The photosensitive silver halide containing silver iodide that is preferably used in the present invention is described by B. Gerafkides, Himi.
Eto Fizik Photographic (Published by Hall Montell) (P, Glafkides.

Chimie et P hysique p
photographique.

Paul Montel) (1967), Photographic Emulsion Chemistry (The Focal Press) (G.
.

F. Durfin, Photoraphic
Emulsion Chemistry, The
Focal press) (1966), Making and Coating Photographic Emulsions (The
Published by Focal Press) (V, L.

Zelikman etal, Making a
nd CoatingPhotoaraphic
Emulsion, The FocalP r
(1964) and others.

That is, 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 silver 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, it is also possible to use the Chondrald double jet method, 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 the method, a so-called monodisperse silver halide emulsion having nearly uniform crystal shape and grain size can be obtained.

The term "monodisperse emulsion" as used in the present invention refers to an emulsion having a grain size distribution in which the variation in silver halide grain size contained in the emulsion is less than a certain ratio with respect to the average grain size as shown below. An emulsion consisting of a group of photosensitive silver halide grains with uniform grain morphology and small grain size variations (
Since the grain size distribution of the monodisperse emulsion (hereinafter referred to as monodisperse emulsion) is almost a normal distribution, the standard deviation can be easily determined, and when the breadth of the distribution is defined by the relational expression, the photosensitive silver halide grains preferably used in the present invention The width of the distribution is 15%
or less, more preferably 10% or less.

Core/shell type photosensitive halogen [arsenal #L AII G, t,
Monodisperse photosensitive halogenation! I! Miko is the core and the shell is IIl! It can be manufactured by m.

In order to form the core into monodisperse silver halide grains, grains of a desired size can be obtained by the double jet method while keeping the pAQ constant. Furthermore, the method described in JP-A-54-48521 can be applied to silver halide emulsions containing highly monodisperse photosensitive silver halide. In a preferred embodiment of the method, a potassium iodide-gelatin aqueous solution and 1.1 ml of ammoniacal nitric acid are added.
Halogenating an aqueous solution 1! ! Gelatin water containing 1 particle @
It is produced by a method in which the additive is added to a liquid at a rate that varies as a function of time.

At this time, the time function of addition/acceleration, l) H, 1) A (1,
By appropriately selecting the temperature and the like, it is possible to obtain a silver halide emulsion containing highly monodisperse silver halide grains for the core.

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

'' bottom margin The thermal phenomenon photosensitive material of the present invention has each layer sensitive to blue light, 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. A multilayer structure is also possible. 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 emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. I can do it.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxazole, and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent.

In addition to the above-mentioned basic nucleus, merocyanine pigments have acidic nuclei such as diohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbylic acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too.

These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination.

Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as those described in US Pat. No. 2.933.
A supersensitizing additive HO agent 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 x 10" mol-1 per mol of photosensitive silver halide or silver halide-forming component.
It is a mole. More preferably, I X 10-4 mol-
1X 10' moles.

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. 52-14
No. 1222, No. 53-36224 and No. 53-37
Publications such as No. 610 and U.S. Patent No. 3.330.6
No. 33, No. 3,794,496, No. 4,105,
No. 451, No. 4,123.274, No. 4.168
．． Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, palmitin! ! Silver, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolethio)acetate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc. Japanese Patent Publication No. 44-26582; Same 4
No. 5-12700, No. 45-18416, No. 45-2
2185Ii4, JP-A No. 52-31728, 52
-137321, JP-A-58-118638, fl
! Silver salts of imino groups such as those described in publications such as t 58-118639@, such as benzotriazole silver, 5-nitrobenzotriazole silver, 5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver,
4-sulfobenzotriazole silver, 4-human 0xybenzotriazole silver, 5-aminobenzotriazole silver,
5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1.2.4-triazole silver, 1H-tetrazole silver, 3-amino-5-
Silver benzylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., and 2 others
-Silver mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, 2
-Mercaptobenzimidazole silver, 3-mercapto-
4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene silver and 5-mebru 7-hydroxy-1°2.3
．． Examples include 4.6-pentazaindene silver. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives, more preferably silver salts of sulfobenzotriazole readers, are particularly preferred.

The organic silver salts used in the present invention may be used alone or in combination of two or more, and isolated ones may be used by dispersing them in a binder by appropriate means, or they may be used in a suitable form. The silver salt may be prepared in a binder and used as is without isolation.

The amount of the organic silver salt used is preferably 0.01 to 500 mol, more preferably 430.1 mol to 100 mol, per mol of photosensitive silver halide.

The present invention can of course be applied to monochrome photothermographic materials, but is preferably applied to color photothermographic materials.

When the heat-developable photosensitive material of the present invention is applied to color, a dye-providing substance is used.

Hereinafter, one dye-donating substance that can be used in the present invention will be explained. The dye-donating substance may be any substance that participates in the reduction reaction of photosensitive silver halide and/or organic silver salt and can form or release a diffusible dye as a function of the reaction, depending on the reaction form. , negative-working dye-donors that act on a positive function (i.e., will form a negative dye image when using negative-working silver halide) and positive-acting dye-donors that act on a negative function (i.e., will form a negative dye image when using negative-working silver halide). (forms a positive dye image when using negative silver halide). Negative dye-donating substances are further classified as follows.

Below margin Releases a diffusible dye when oxidized Release type compound　　Formation type compound Each dye-providing substance will be further explained.

As the reducing dye releasing compound, for example, general formula (17)
Examples include compounds represented by:

General formula (17) % formula % In the formula, Car is a reducing substrate (so-called chirelia) that is oxidized and releases a dye upon reduction of the photosensitive silver halide and/or an organic radical used as necessary. ,D
ye is a diffusible dye residue.

The reducibility of the above! ! Specific examples of elementary releasing compounds include JP-A-57-179840, I-58116537, I-59-80434, I-59-65839, and I-5.
No. 9-71046, No. 59-87450, No. 59-8
No. 8730, No. 59-123837, No. 59-165
No. 054, No. 59-165055, and the like, and include, for example, the following compounds.

In the margin below, exemplified dye-donor substances 0C16 (n) ■ OCl. ``ss (n)'' Another reducing compound has the general formula (1
List the compounds shown in 8).

General formula (18) In the formula, A+ and A2 each represent a hydrogen atom, a human [loxy group, or an amino group, and Dye has the same meaning as Dye shown in general formula (17). Specific examples 1-1 of the above compound are shown in JP-A-59-124329.

As a coupled dye-releasing compound, general formula (19
) are listed.

General formula (19) % formula % In the formula, Cp+ 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 21i1! It is a bonding group for i, and the bond between CD+ and J is cleaved by reaction with an oxidized form of a reducing agent. nl represents O or 1, Dye is general formula (17)
It has the same meaning as defined in . In addition, CD1 is preferably directly substituted with a ballast group of a famous actor in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 carbon atoms depending on the form of the photosensitive material used.
or more (more preferably 12 or more) m groups, or hydrophilic groups such as sulfo groups or carboxy 4, or 8 or more (more preferably 12 or more)
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 particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (19) include JP-A-57-186744 and JP-A-57-12259.
No. 6, 57-160698@, 59-174834
@, No. 57-224883@, No. 59-159159, and Japanese Patent Application No. 104901/1983, reprinted in each specification S, and include, for example, the following compounds.

Exemplary dye-providing substances CH3 ■ Coupled dye-forming compounds include bifurcated (20
) are listed.

General formula (20) % formula %) In the formula, CI)2 is an organic M that can react (coupling reaction) with the oxidized form of the reducing agent to form a diffusible dye.
(so-called coupler residue), F represents a divalent bonding group, and B represents a ballast group.

The molecular weight of the coupler residue represented by CI)2 is preferably 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed.

Further, the ballast group is preferably the same as the ballast group defined in general formula (19), 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.

The coupled dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (21).

General formula (21) % formula %) In the formula, CI)2 and F have the same meaning as defined in general formula (20), Y represents an alkylene group, arylene group, or aralkylene group, and 2 is 0 or 1, 2
represents @IJ of 211i, and does not represent an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds represented by general formulas (20) and (21) include JP-A-59-42
No. 4339, No. 59-181345, Patent Application No. 1982-1
No. 09293, No. 59-1796574, No. 59-18
No. 1604, No. 59-182506, No. 59-182
50T@, etc., and include, for example, the following compounds.

Below margin Exemplary dye-donor substances 0CHC1nHn ■ OOH ■ polymer 0H ! :60% by weight y: 40il amount% @ (i’H3 χ:90 weight +-1 ’;d:’9o heavy↑・/.

In more detail, the coupler residue defined by Cpl or C112 in the above general formulas (19), (2o) and (21) is preferably a group represented by the following general formula.

General formula (22) General formula (23) General formula (4) General formula (25) My,
l (Gas General formula (28) General formula (29) General formula (3o) General formula (31) In the formula, R
33, R34, Rss and R36 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group , a carbamoyl group, a sulfamoyl group, an acyloxy group, an amino group, an alkoxy group, an aryloxy group, a siam L ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, which may further include a hydroxyl group, a carboxy group , a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, an aryloxy group, 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 CDt and CI)2, and as mentioned above, in <CI++, one of the r11 substituents is preferably a ballast group, and in C112, it is preferable to In order to increase the molecular weight, the substituents are preferably selected so that the molecular bond is 100 or less, more preferably 500 or less.

As a positive dye-donating substance, for example, the following general formula (3
There is an oxidizable dye-releasing compound represented by 2).

General formula (32) In the formula, Wl represents a group of atoms necessary to form a quinone ring (which may have a substituent on this ring), and R37 represents an alkyl group or a hydrogen atom. represents a group or a hydrogen atom, R39 represents an oxygen atom or r represents O or 1, and Dye has the same meaning as defined in general formula (17). A specific example of this compound is JP-A-59-1669.
No. 54, No. 59-154445, etc., and include, for example, the following compounds.

Exemplary dye-donating substance Anzu, □□□ CHa Another positive dye-donating substance is represented by the following general formula (33)
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by .

General formula (33) In the formula, W2 represents a group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R3
7. rSEqDye has the same meaning as defined in general formula (32). A specific example of this compound is JP-A-59-12
43299, No. 59-154445, etc., and include the following compounds.

Exemplary dye-donating substance■ Still another positive dye-donating substance '1'1 is a compound represented by the following general formula (34)? can be lost.

General formula (34) In the above formula, W2, R3, -I, and Dye have the same meanings as defined in general formula (33).

Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds.

Exemplary Dye Donor Substances - More details regarding the residues of the diffusible dyes represented by the above general formulas (17), (18), (19), and the formula %). The residue of the diffusible dye preferably has a molecule m of 800 or less, more preferably 600 or less, for the sake of dye diffusivity, and includes azo lfi W, azomethine dye, anthraquinone dye, naphthoquinone dye, and styryl dye. , nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like. These dye residues may be in a temporary short-wavelength form that can be multicolored during thermal development or transfer.

In addition, these residual pigments are used for the purpose of increasing the light resistance of both images, for example, in JP-A-59-48765 and JP-A-59-1243.
This is a preferred form of the chelatable dye residue described in No. 37.

These dye-providing substances may be used alone or in combination of two or more. The use m is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination of two or more, whether the photosensitive layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers, etc. Although it may be determined accordingly, for example, the amount of use can be from o.oosg to 50 g per 112, preferably from o.oosg to 10 g.

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. ,
(tricresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.) and then neutralized with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.). Alternatively, it can be used as a dispersion using a ball mill with an aqueous solution of a suitable polymer (eg, gelatin, polyvinyl butyral, polyvinylpyrrolidone).

As the reducing agent used in the heat-developable photosensitive material of the present invention, those commonly used in the field of heat-developable photosensitive materials can be used, such as those disclosed in U.S. Pat.
, 7G1, 270, No. 3.7G4, 328 each posting N1 and RD No. 12146, No. 1510
3. Same No.

15127 and JP-A-56-27132, p-phenylenediamine type and p-aminophenol type developing agents, phosphoroamide phenol type and sulvonamide phenol type developing agents and main agents, and hydrazone type O main agents for color development. can be mentioned. Also, U.S. Patent No. 3,
The color-developing agent precursors described in Japanese Patent Application Laid-open Nos. 342,599, 3,719,492, JP-A-53-135628, and JP-A-54-79035 can also be used advantageously.

As a particularly preferred reducing agent, JP-A-56-14613
Examples include reducing agents represented by the following general formula (35), which are described in No. 3 Meigou Zan.

General formula (35) In the formula, R40 and R*I are hydrogen atoms, or have 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent.
represents an alkyl group, and R40 and R+1 may be closed to form a heterocycle. R42, R43-R44 and U
%r is a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 30 (preferably 1 to 4) that may have a substituent. ) represents an alkyl group, and R42 and R40 and R44 and R41 may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (35) is
It is a compound containing a basic nitrogen atom that can form a salt with an acid, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. ,
Examples include imidazole. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. As the salt of the nitrogen-containing 1'T base, the above-mentioned 11-base PIA base hydrochloride salts (eg, 1M salt, sulfate, 611 acid salt, etc.) are preferably used.

On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond.

Below is a margin.Next, preferred specific examples of the reducing agents represented by the above general formulas (3) are shown below.

(R-1) (R-2) (R-3) (R-4) (R-5) (R-6) (R-7) (R-8) (R-9) H3 (R-10 ) (R-11) (R-12) (R-15) (R-16) (R-17) (R-18) (R-19) F3 (R-20) (R-21) (R- 22) (R-23) The reducing agent represented by the above general formula (35) can be reduced by a known method such as Houben Peil, Methoden der Organizien Hemi, Band XI/2 (Hoube
n-Weyl, Methoden der Ora
anischen Chemie, Band X
I/2) can be synthesized according to the method described on pages 645-103.

Other reducing agents as described below can also be used.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulbonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2.6-dipromo 4-
(11-toluenesulfonamide)phenol, etc.], or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,11-binaphthyl, 6,6-dinito D-
2,2'-dihydroxy-1,1'-binaphthyl, 4,
4'-dimethoxy-1,1'-dihydroxy-2,2'
-binaphthyl, bis(2-hydroxy-1-naphthyl)
methane, etc.], methylene bisphenols [e.g. 1.1
-bis(2-hydroxy-3,5-dimethylphenyl)
-3゜5.5-trimethylhexane, 1.1-bis(2
-Hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis<2-hydroxy-3,5
-di-tert-butylphenyl)methane, 2,6-methylenebis(2- and droxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol, α-phenyl-α, α-bis(2-and-droxy-3,5-di-tert-butylphenyl)methane, α-phenyl-α
, α-bis(2-hydroxy-3-tert-butyl-
5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5.5-tetrakis(2-hydroxy-
3,5-dimethylphenyl)-2,4-ethylpentane, 2,2-bis(4-hydroxy-3゜5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3
-methyl-5-tert-butylphenyl)propane,
2.2-bis(4-hydroxy-3,5-tert)
-butylphenyl)propane, etc.], ascorpinic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide used, the type of organic acid silver salt, and the type of other additives, etc. φ is usually 1 mole of photosensitive silver halide. in the range of 0.01 to 1500 mol,
Preferably it is 0.1 to 200 mol.

Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic 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 vinyl pyrrolidone polymer may be polyvinyl pyrrolidone, which is a homopolymer of vinyl pyrrolidone, or a copolymer (graft copolymer) with one (or two or more) of Ike's seven polymers that can be copolymerized with vinyl pyrrolidone. ).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 4.
00.000. Monomers that can be copolymerized with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and their alkyl esters, vinyl alcohols, vinyl imidazoles, (meth)acrylamides, and vinyl carbinols. , vinyl alkyl ethers, and the like, but it is preferable that at least 20% (la%, the same applies hereinafter) of the composition ratio is polyvinylpyrrolidone. A preferred example of such a copolymer has a molecular group of 5.00
0 to 400.000.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the above binder, gelatin preferably accounts for 10 to 90% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
Gelatin and molecules It 1,000-400,000 (
7) Mixture of polyvinylpyrrolidone and one or more other polymeric substances, gelatin and Molecule II 5,000~
A mixture of 400,000 vinylpyrrolidone copolymer and one or more other polymeric materials is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene brecol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These may be contained in an amount of 0 to 85%, preferably 0 to 70%.

Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to apply it onto a support and then crosslink it (including the case where the crosslinking reaction proceeds by spontaneous release).

Binder usage is usually - 0 for 112
．． 05Q to 50g, preferably 01g to 109.

The support used in the heat-developable photosensitive material of the present invention includes:
If it falls over, it will reflect on synthetic plastic films such as polyethylene film, cellulose acetate film, polyethylene terephthalate film, and polyvinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper, and resin coated paper, and the synthetic plastic films mentioned above. Examples include a support provided with a layer.

In particular, it is preferable that various heat solvents be added to the heat-developable photosensitive material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably solid, semi-solid, or liquid at room temperature (preferably with a boiling point of 100°C or higher at normal pressure, more preferably 150°C). above) which dissolve or melt in the binder by heating, preferably urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.), Examples include polyhydric alcohols (eg, 1.5-bentanediol, 1.6-bentanediol, 1.2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), and polyethylene glycols. For a detailed example, see the patent application 1986-10.
4249. 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 heat-developable photosensitive material of the present invention, if necessary.

For example, as a development accelerator, U.S. Patent No. 3,220,8
No. 40, No. 3,531,285, No. 4,012,
No. 260, No. 4,060,42C1, No. 4,08
No. 8,496, No. 4,207゜392@each specification, R
D No. 15733, No. 0.15734, No. 15776, alkali release agents such as urea and guanidium trichloroacetate described in JP-A-56-130745, JP-A-56-132332Q, etc.;
5-12700 Organic Acids, U.S. Patent No. 3.667
, No. 959 (7) -Co+, -802-, -8o-
Non-Aqueous Polar Solvent Compounds with W, U.S. Pat. No. 3.43
8.776, Melt Former-1 U.S. Patent No. 3,
There are polyalkylene glycols described in No. 666.411 and JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 46-607
No. 7, No. 49-5019, No. 49-5020, No. 49-91215, No. 49-1077゛27, No. 50-2524, No. 50-67132, No. 50-
No. 67641, No. 50-114217, No. 52-33
No. 722, No. 52-99813, No. 53-1020, No. 53-55115, No. 53-76020, No. 5
No. 3-125014, No. 54-156523, No. 54
-156524, 54-156525, 54-
No. 156526, No. 55-4060, No. 55-406
14, Publications such as No. 55-32015, West German Patent No. 2.140.406, West German Patent No. 2.147.063,
No. 2,220,618, U.S. Patent No. 3,080,25
No. 4, No. 3, No. 847.612, No. 3. γ82,9
No. 41, No. 3.994.732, No. 4,123,
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which are compounds described in the specifications of No. 282, No. 4,201,582, etc.
2,3-dihydro-phthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl 2H-1,3-benzothiazine -2.4- (3H)dione, benzotriazine, mercaptotriacyl,
Dimercabutotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and at least acids or acid anhydrides such as phthalic acid, naphthalic acid, etc. Combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, etc. can be mentioned.

Also, JP-A No. 58-189628 Tan, No. 58-1934
3-amino-5-mercapto-1'. described in Publication No. 60. 2.4-triazoles, 3-acylamino-
5-mercapto-1,2,4-triazoles are also effective.

In addition, as a stabilizer, a print-out preventive agent may be used at the same time, especially after processing, for example, as disclosed in JP-A No. 48-45228, JP-A No. 50-119624, and JP-A No. 50-120328.
Halogenated hydrocarbons described in No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2
-Bromo-2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2. 4
-es(tribromomethyl)-6-methyltriazine, and the like.

Also, Special Publication No. 46-53938, Special Publication. Opening/closing 50-5432
Post-treatment may be carried out using a sulfur-containing compound as described in No. 9, Transcription Publication No. 50-77034.

Furthermore, isothiuronium stabilizer precursors described in U.S. Patent Nos. 3,301,678, 3,506,444, 3,824,103, and 3,844,788 Also, U.S. Patent Nos. 3.669.670 and 4,012,260
No. 4,060,420, etc. may be contained.

Also, sucrose, NH4Fe (SO4)2 ・12H2
A water release agent such as No. 0 may also be used;
Heat development may be carried out by supplying water as in No. 6-132332.

In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may further contain various additives such as spectral sensitizers, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents. agents, coating aids, etc. are added.

The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (3) in one photosensitive layer.
) An organic silver salt, (4) a binder, and (5) a dye-providing substance are preferably contained.

However, these do not necessarily need to be contained in a single constituent layer; for example, the photosensitive layer may be divided into two layers, and the above (1)
), (2), (3), and (4) are contained in the photosensitive layer on one side, and the dye-donating substance (5) is contained in the layer on the other side adjacent to this photosensitive layer. It may be contained separately in two or more photographic constituent layers, as long as it is in a state where it can react with.

Further, the photosensitive layer may be provided in two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and one or more photosensitive layers having different color sensitivities may be provided. It may have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and a middle layer.

Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or U.S. A photosensitive material can be prepared by a coating method such as the hopper coating method described in Japanese Patent No. 3,681.294.

Additionally, if desired, 212 or more can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The above-mentioned components used in the photographic constituent layer of the heat-developable photosensitive material of the present invention are coated on a support, and the coating thickness after drying is preferably 1 to 1,000 μm, more preferably 3 to 2 μm.
It is 0 μm.

After the heat-developable photosensitive material of the present invention is imagewise exposed as it is,
Usually 80°C to 200°C, preferably 120°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. The latent image is obtained by imagewise exposure of a radiation IHIil containing visible light. Light sources commonly used for regular color printing, such as tungsten lamps,
Mercury lamps, xenon lamps, laser beams, CRT beams, etc. can be used as light sources.

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, to provide a conductive layer in the photosensitive material of the present invention or in the image receiving element for thermal transfer (m<element) to utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of preheating and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, continuously increasing, decreasing, or repeating, and even discontinuously. Although heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The image receiving member used in the present invention only needs to have the ability to receive the dye released or formed by thermal development, and may be a mordant used in dye diffusion transfer type photosensitive materials or JP-A-57-2
It is preferable to use a heat-resistant polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower as described in Japanese Patent No. 07250 or the like. - Specific examples of the mordant include:
Nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, U.S. Patent No. 2,548,5
No. 64, No. 2.484.430, No. 3.148.06
No. 1, vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 3,756,814, dialkylamino group-containing polymers disclosed in U.S. Pat.
Aminoguanidine derivatives disclosed in , 882.156, covalent reactive polymers disclosed in JP 54-137333, U.S. Pat. No. 3,625,694, U.S. Pat. British Patent No. 1,277.4
No. 53, same 2. Off, a mordant crosslinkable with gelatin and the like as disclosed in U.S. Pat. No. 3,958.
No. 995, No. 2,721,852, No. 2,798, 0
Aqueous sol type mordant disclosed in No. 63, Japanese Patent Application Laid-open No. 1983
-61228, a water-insoluble mordant disclosed in U.S. Patent No. 3.788.855, West German Patent Application (OLS)
No. 2,843,320, Japanese Patent Application Publication No. 53-30328,
No. 52-155528, No. 53-125, No. 53
-1024, 54-74430, 54-124
No. 726, (tq 55-22766, U.S. Pat.
, No. 271.148, Special Publication No. 55-29418, No. 5
No. 6-36414, No. 57-12139, RD 12
045 (1974) can be mentioned.

Particularly useful mordants are polymers containing ammonium salts,
Polymer containing quaternary amino groups as described in US Pat. No. 3,709,690. Examples of polymers containing ammonium salts include polystyrene-N,N,N-tri-0-hexyl-N-vinylbenzylammonium chloride, where the ratio of styrene and vinylbenzylammonium chloride is 1:4 to 4:1; Preferably the ratio is 1:1.

A typical dye diffusion transfer receiver (glFJ) is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a support.

Examples of the heat-resistant polymeric substance include molecules 112.
000 to 85,000 polystyrene, polystyrene derivatives with substituents having 4 or less carbon atoms, polyacetals such as polyvinylcyclohexane, polyvinylbenzene, poly, vinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral. polyvinyl chloride, chlorinated polystyrene, polytrichlorofluorinated ethylene, polyacrylonitrile, poly N, N-dimethylacrylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, poly Acrylic chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-
Examples include polyesters such as 2-cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrites, polyamides, and cellulose acetates. In addition, the Polymer Handbook 2nd edition (Polymer Handbook
2nd ed, ), G.A. Brandrup, E.H. Inmargt@(J, 3ra
ndrup, E, H, Immergut
), published by John Wiley & Sons (J
Also useful are synthetic polymers with glass transition temperatures of 40° C. or higher, such as those described in W. Iley & Sons. These polymeric substances may be used alone or in combination of two or more as a copolymer.

Particularly useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, heptamethylene diamine and diphenic acid, heptamethylene diamine and isophthalic acid, Examples include polyester made from a combination of diethylene glycol, diphenylcarbonbis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, polycarbonate, and vinyl chloride. These polymers may be modified. For example, cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol,
Polyethylene terephthalate using 1,2-dicarbome-1-xy-4-benzenesulfonic acid or the like as a modifier is also effective. Among these, particularly preferred are the
Examples include a layer made of polyvinyl chloride as described in Japanese Patent Application No. 8-97907, and a layer made of polycarbonate and a plasticizer as described in Japanese Patent Application No. 128600/1983.

The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like passive layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer by a member (for example, a film) made of the above-mentioned polymer alone (also used as an image-receiving layer support).

Furthermore, the image-receiving layer may be constructed by providing an opaque layer (reflective FfJ) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer receives a transferred color image, and a reflective color image can be obtained by viewing the layer from the transparent support side.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples. ! ! Mr. i is not limited to these.

Example 1 [Emulsion A: Made by A] Emulsion A was made by J by the following method. Japanese Patent Application V157-9
2523, 20 g of ossein gelatin at 50° C. using the mixer shown in Specification Q of No. 57J2524.
1) Simultaneously add 500 vQ of an aqueous solution B containing 130.9 fJ of potassium bromide and 500 wI 2 cn of an aqueous solution containing 1 mole of silver nitrate and ammonia to A solution containing 1000 i12 of distilled water and ammonia. Al
1 was added while keeping it constant. The shape and niceness of the emulsion grains to be prepared were controlled by controlling the pH, pA, and the addition rates of solutions B and C, and by adjusting the tIl, a silver bromide emulsion was obtained.

The silver halide grains of the silver bromide emulsion prepared by JQ were octahedral grains with an average grain size of 03 μm and a monodispersity of 8%.

This emulsion was washed with water and treated with 1152 salt. The yield R of the emulsion is aoo
It was wx.

[Preparation of Emulsions B and C] Two types of emulsions B and C having different silver iodide contents were prepared by the following method. Ossein gelatin 20C1, distilled water 100011 were added to the emulsion in the same manner at 50°C.
Solution A, in which 2 and ammonia were dissolved, was added to a specified concentration of potassium iodide and potassium bromide (for emulsion B, potassium iodide G, 04 g, potassium 91 chloride 130.9 (1), for emulsion C, iodide Potassium 11.62g, potassium bromide 13
B liquid 500 consisting of an aqueous solution containing 0.9 (1)
d and C solution 500-, which is an aqueous solution containing 1 mol of silver nitrate and ammonia, were simultaneously added while keeping pA (+ constant).The shape and noise of the emulsion grains to be prepared are I)H, I)A (A silver iodobromide emulsion was obtained by controlling the addition speed 11 of I, Bl, and C solutions. In this way, the silver iodobromide emulsion had the same regular octahedral shape and only the silver iodide content was responsible. 1L formulations 8 and C were washed with S11!yJ. (The monodispersity of each emulsion was 9%) These emulsions were washed with water and desalted, respectively.

The yield of each emulsion was 800 yen.

[Preparation of Emulsions E and F] Thirty-one types of core/shell emulsions differing in silver iodide content and grain size were prepared by the following method.

At 50°C, JP-A No. 57-2523, No. 57-
92524@Specification 4 Using the stirring chamber shown in Specification 4, add potassium iodide and 1 hpotassium odor to a solution A in which ossein gelatin 20 (1, m distilled water + 1 fl OOO and ammonia) was dissolved at a predetermined concentration (emulsion emulsion). For use, potassium iodide 11,
62 (1, potassium bromide 130.9Q, for emulsion B potassium iodide 11.62jl, potassium bromide 130.9
Q. For emulsion B, an aqueous solution containing potassium iodide 33.2 (1, potassium bromide 119, OIJ) 500
Solution B of v12 and Solution C of aqueous solution 50011 containing 1 mol of silver nitrate and ammonia were simultaneously added while keeping the pAg constant. The shape and size of the particles of the core emulsion to be prepared are determined by adjusting the pH, pAo, and the addition rate of liquids B and C.
Adjustment was made by adjusting II 1m. In this way, core emulsions having the same regular octahedral shape but different grain sizes and silver iodide contents were prepared. (The monodispersity of each core emulsion was 8%.) Next, the silver halide grains obtained above were used as cores and coated with a silver halide shell in the same manner as described above. Core/shell type emulsions D to F having the same regular octahedral shape but different grain sizes and silver iodide contents were prepared.

These emulsions were washed with water, desalted, and so
i'. Table 1 summarizes the properties of the six types of emulsions A to F prepared in this manner.

Margin table below 1 Silver iodide content Shell grain emulsion (mol%) Thickness Size Core Shell
(μ11) (μ]) A OO, 3 340, 3 G 7 0.3D
7 2 0.04 0.3E 7
2 0.05 0.5F 20 4
0.04 0.3 [Photosensitive silver halide dispersion made by W4] The six types of silver halide emulsions prepared above were mixed with the following sensitizing dye (1) and 4-hydroxy-6-methyl-1,3, A photosensitive silver halide dispersion having the following composition was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of 3a,7-chitrazaindene.

Silver halide < ta) 381 (J gelatin 85 (1/2820tR sensitizing dye (1) ・N(CtHi)s [Preparation of organic silver salt dispersion] 5-methylbenzotriazole and silver nitrate were dissolved in water - 28.8 g of 5-methylbenzotriazole silver obtained by reaction in an alcohol mixed solvent, 16.00 g of poly(N-vinylpyrrolidone) and 1.33 (l) of 4-sulfobenzotriazole sodium salt were mixed in an alumina ball mill. The organic silver salt dispersion liquid 200d was prepared by dispersing and adjusting the pH to s.

[Preparation of dye-providing substance dispersion]

Exemplary dye-providing substance ■35.5 (7 to ethyl acetate 200-
Dissolved in Alkanol XC (manufactured by DuPont) 5% by weight
Aqueous solution 124iN, phenylcarbamoylated geladine (
Rousslow Co., Type 17819p C) Gelatin aqueous solution 72 containing 30.50 (h12) and dispersed with an ultrasonic homogenizer, and after distilling off ethyl acetate, DH5
, 5 to 795 v (l) and dye-providing substance dispersion (1
) was prepared.

[Preparation of developer dispersion] Exemplary reducing agent (R-11) 23.3o, the following development accelerator 1.10i7, poly(N-vinylpyrrolidone) 14
．． A developer dispersion liquid was prepared by dissolving 6 g of the following fluorine-based surfactants o and sog in water and adjusting the pH to 2501j2.

Development accelerator CH, -CH=CH2 Surfactant (-=2 tm, tt3) [Preparation of photothermographic material] Three types of photosensitive silver halide dispersions A, C, and D prepared above 6.00mR1 organic silver salt dispersion 12.5tf, dye-providing substance dispersion 39.81fl, developer dispersion 12.
5 dl and a 2 x 10 to 2 molar aqueous solution of the compound shown in Table 2 below as an antifoggant were mixed, and to this mixture was added a hardening agent of 9 tora(vinylsulfonylmethyl)methane and taurine in a ratio of 1:1 (by weight). ) and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin so that the tetra(vinylsulfonylmethyl)methane content was 3% by weight) was mixed with polyethylene glycol 300 (Kanto 3.80g (manufactured by Kagakusha)
After the addition, 1.5 g of silver was deposited on a photographic polyethylene terephthalate film with a thickness of 180 μm that had been subbed.
760/f, and a protective layer made of a mixture of the phenylcarbamoylated gelatin and poly(N-vinylpyrrolidone) was further provided thereon to obtain heat-developable photosensitive materials samples F11 to F15 shown in Table 2. Ta.

[Creation of image-receiving element] Photographic Banitaki 1 (on top, polyvinyl chloride (n=1,
1. Apply a trihydrofuran solution of 100, Wako Tsuyaku). [Paris] An image-receiving element made of vinyl uride with a diameter of 12 (1/a2) was prepared.

The heat-developable photosensitive material prepared above was exposed to +, 600C, M, and S through a step wedge, and together with the image-receiving element was heated at 150C in a heat development machine (manufactured by Dipero Tuba Module 277.3M). After 1 minute of thermal development, the photosensitive material and the image receiving element were quickly peeled off, and a magenta colored step image (7) was left on the polyvinyl chloride surface of the photosensitive material.

The marginal reflection density of the obtained negative image is measured by 'f: degree meter (PDA-
65, manufactured by Konishiroku Photo Industry ■). Table 2 below shows the maximum power, relative sensitivity, and minimum hardness (fog).

Margin Table 2 below: However, the comparative antifoggant (a) used in Table 2
The construction of l1ia is as follows.

Further, in Table 2, the Kan34 sensitivity is the reciprocal of the exposure matrix that gives an f:J degree of fog + 0.3, and is the reciprocal of the exposure standard for sample No.

Relative ((represented by j) where the value of 1 is 100.

From the results in Table 2, the test tl (with no antifoggant added)
Compared to Nos. 1 to 3), the samples containing comparative antifoggants (Nos. 4 to 5) showed almost no effect of lowering the minimum density (fog), whereas the compounds of the present invention 1 (No, 6 to 15), the minimum r degree was lowered without reducing the maximum concentration too much, and
It can be seen that the compound of the present invention is highly effective as an effective antifoggant. Also, g
It can be seen that a is also better than Comparative Test 1.

Furthermore, looking at the characteristics of the emulsions, we found that in contrast to the sample Fl (No. 10) of the present invention using a bromide root emulsion, the present invention using a silver iodobromide emulsion containing silver iodide. sample (No. 1
1), a significant increase in sensitivity was observed, and sample f1 (No. 1) of the present invention using a silver iodobromide core/shell emulsion
, 12-15) further improved the sensitivity, indicating that the compounds of the present invention function as effective antifoggants.

Example 2 [WA1 of photosensitive silver halide dispersion] The following sensitizing dye (2) was added to the emulsion A% B and F prepared in Example 1.
and 4-hydroxy-〇-methyl-1.3.38.7
- A photosensitive silver halide dispersion having the following composition was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of chitrazaindene.

Sensitizing dye (2) Silver halide (converted to silver) 381g gelatin 85Q/ 2820II12
[Preparation of dye-providing substance dispersion] Exemplary dye-providing substance ■30. Dissolve Og in 30.0 μl of tricresyl phosphate and 90.0 μl of ethyl acetate,
The same as in Example 1, it was mixed with 460 kg of aqueous Sera 1 solution containing a surfactant, dispersed with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to make the volume 5001 ft. ) was prepared as vlI.

[Preparation of heat-developable photosensitive material] Photosensitive silver halide dispersion 40 prepared by 'JI11J' above.
．． 0mR1 Stepped silver salt dispersion prepared in Example 1 25,
omβ, 50.0 t of the dye-providing substance dispersion prepared above
j2 and then polyethylene glycol 300 (manufactured by Kanto Kagaku Co., Ltd.) 4y2og as a heat solvent, Example 1
A hardener solution similar to
．． 01β and 2,6-dichloro-p-aminophenol in a 10% methanol solution V120.0- were added onto a photographic polyethylene terephthalate film having a thickness of 180 μm and subjected to undercoating. The photothermographic materials shown in Table 3 below were coated so as to give a heat-developable photosensitive material of 4 samples 16 to 33 on a tatami mat.

[Preparation of image-receiving element] The following layers were sequentially coated on a polyethylene terephthalate film having a thickness of 100 μm to prepare an image-receiving element.

(1) Layer made of polyacrylic acid.

(7,00!II/l”) (2) A layer consisting of cellulose acetate.

(4,00(+/f) (3) Styrene and N-benzyl-N,N-dimethyl-N
- A layer consisting of a 1:1 comonomer J3 of (3-maleimidopropyl)ammonium chloride and gelatin.

The heat-developable photosensitive material samples 16 to 33 were exposed to 1,600 C, M, and S through a step wedge.
After heating for 1 minute on a heat block at 50°C, immersed in water] s12, combined with the β summary of s12, 50
℃, 500 g to 800 μm/C12 was applied for 30 seconds, and the transmission was measured at 04 degrees using a densitometer (PDA-65).
, was measured using Konishiroku Photography 2 Co., Ltd. The maximum and minimum densities (fog) and relative sensitivities obtained are not shown in Table 3 below.

The antifoggant (a) used in Table 3 is the same as that used in Example 1. In addition, the relative sensitivity is the reciprocal of the exposure value that gives a ci degree of fog + 0.3, and the sample N
It is expressed as a relative value with 16 companies as 100.

Margin table 3 below! As is clear from the conclusion in Figure 3, using dye donor 7''I, which is a well-developed compound that reacts with photosensitive halogenated IR to release aqueous dye upon heating. Also, it can be seen that the same results as in Example 1 are obtained every time a cup is taken.

That is, the sample to which no antifoggant was added (N +116
~19), a sample with a comparative antifoggant added (
No. 20) has almost no effect of lowering the minimum 1 degree (fog), whereas the samples containing the compound of the present invention (Nos. 21 to 33) have no effect of lowering the minimum 1 degree (fog) without significantly lowering the maximum concentration. The opening degree is lowered (especially No. 26-33)
1L antifogging agent in which the compound of the present invention is effective
It can be seen that 'JI+' is used as an agent. Further, it can be seen that the sensitivity is also better than that of the comparative sample PL.

Furthermore, focusing on the characteristics of the emulsion, the sample of the present invention using a silver q-dide emulsion (No. 27) was compared to the sample of the present invention using a silver iodobromide 7L agent containing silver iodide. Sample (No. 2
8.29, 32.33), a significant increase in sensitivity was observed, and the sample of the present invention (NO, 30°31) using a silver iodobromide core/shell 1 binder showed an even greater sensitivity increase. It can be seen that the compounds of the present invention are effective antifoggants for whitening.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedure Arrival 17 tl Sannori (Voluntary) ffl To December 5, 1961 Director-General of the Office of Revision Black 1) Akio-dono 1, Indication of the Case 1985 Special Edition' [Application No. No. 205129 No. 2, Name of the invention Heat development (3) Photosensitive material, 11 3, Relationship with +'t Applicant's address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
11th Shishi 4, Agent 102 Address 111 Kudankita 4-chome, Chiyoda-ku, Tokyo January Kudan-
Kuchisaka Building Telephone: 263-9524 6. Contents of the Amendment The detailed description of the invention will be corrected as follows.

(1) General formula (12
) is written as follows.

(2) Delete Exemplary Compound No. (26) on page 21 of the specification.

(3) On page 25, lines 14 to 15 of Akizakeri, the statement "Adjusted by...method..." was changed to "Prepared by...method..."
・J and correction blade.

(/I) Replace Table 3 on page 107 of the specification with (attached sheet).

that's all (Attachment) Table 3

Claims (3)

[Claims] (1) In a heat-developable light-sensitive material having at least a photosensitive silver halide, an organic silver salt, a reducing agent, and a binder on a support, the heat-developable light-sensitive material further comprises the following general formula (1).
) A photothermographic material characterized by containing a compound represented by: General formula (1) Represents an acid group or its salt. (2) In the compound represented by the general formula (1), X
The heat-developable photosensitive material according to claim 1, wherein the development inhibitor residue is a compound having an -SH group. (3) In the compound represented by the general formula (1), X
the development inhibitor residue is a nitrogen-containing heterocyclic residue, and R
The heat-developable photosensitive material according to claim 1, wherein is a sulfo group or a salt thereof.